KR20010050903A - Positive resist composition - Google Patents

Abstract

PURPOSE: A chemical amplification type positive photoresist composition is provided to ensure improved edge roughness of a pattern and to give an excellent resist pattern profile with high sensitivity. CONSTITUTION: A positive type resist composition contains a compound which generates an acid when irradiated with active light or radiation and a resin containing an alkali-soluble group protected with at least one specified alicyclic hydrocarbon-containing partial structure, having 5% or less monomer content based on the entire pattern area by gel permeation chromatography(GPC) and having the rate of dissolution in an alkali developing solution increased by the acid.

Description

Positive Resist Composition {POSITIVE RESIST COMPOSITION}

The present invention relates to a positive resist composition for use in ultramicrolithography processes such as the manufacture of ultra-LSI and high-capacity microchips, and other photographic processes. More particularly, it relates to a positive resist composition in which edge roughness is eliminated and retains excellent profile and high sensitivity.

In recent years, the degree of integration of integrated circuits has increased more, and in the manufacture of semiconductor substrates such as ultra-LSI, processing of ultrafine patterns having a line width of 1/2 micron or less is required. In order to meet this need, the wavelength used for the exposure apparatus used for photolithography has become shorter, and the use of excimer laser light (XeCL, KrF, ArF, etc.), which is a short wavelength in far ultraviolet rays, has now been considered.

Chemical amplification resists are used for pattern formation in lithography in this wavelength region.

In general, chemically amplified resists can be roughly classified into three types, namely two-component, 2.5-component, and three-component systems. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin that decomposes under the action of an acid and retains in one molecule a group (called an acid-decomposable group) that increases solubility in an alkali developer of the resin. The 2.5 component system contains a low molecular weight compound which further has an acid-decomposable group in the bicomponent system. A three component system contains an acid generator, alkali-soluble resin, and the said low molecular weight compound.

The chemically amplified resist is suitable for ultraviolet or far-infrared ray photoresist, but it is necessary to correspond to the required performance in use.

As a photoresist composition for an ArF light source, a resin in which an alicyclic hydrocarbon site is introduced in order to impart dry etching resistance has been proposed. The harmful effects caused by the introduction of the alicyclic hydrocarbon site are very hydrophobic, which makes it difficult to develop in the tetramethylammonium hydroxide (TMAH) aqueous solution, which is conventionally used as a resist developer. The phenomenon can be found that the resist may peel off.

In order to prevent such a resist hydrophobization, a response such as mixing an organic solvent such as isopropyl alcohol in the developing solution is examined, and although the end result is obtained, there are problems such as expansion of the resist film and complexity of the process. Is not necessarily solved. In order to improve the resist, many measures have been taken to supplement various alicyclic hydrocarbon sites which are hydrophobic by introducing hydrophilic groups.

Japanese Patent Laid-Open No. 10-10739 discloses an energy-sensitive resist material including a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in a main chain, maleic anhydride, and a monomer having a carboxyl group. Japanese Patent Laid-Open No. 10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in a main chain and a radiation-sensitive acid generator. Japanese Patent Laid-Open No. 11-109632 discloses the use of a resin containing an alicyclic functional group and an acid-decomposable group containing a polar group as a radiation photosensitive material.

As described above, the resin containing the acid-decomposable group used as the photoresist for far ultraviolet light exposure generally contains aliphatic cyclic hydrocarbon groups in the molecule. For this reason, the resin becomes hydrophobic, which causes a problem. Various means for improving the above have been examined variously, but the said technique is still inadequate and the improvement is calculated | required.

Recently, as the miniaturization of semiconductor chips is required, the design patterns of these fine semiconductors have reached the fine region of 0.13 to 0.35 mu m. Therefore, in such a composition, there is a problem that the resolution of the pattern is disturbed by factors such as the edge roughness of the line pattern. Here, the edge roughness means that the edges of the top and bottom of the line pattern of the resist are irregularly changed in the direction perpendicular to the line direction due to the characteristics of the resist, so that the edges are uneven when viewed from above. Say.

As mentioned above, in the known technique of the conventional photoresist composition, the edge roughness of the pattern was observed, and a stable pattern was not obtained, so improvement was necessary.

It is therefore an object of the present invention to provide a highly sensitive chemically amplified positive photoresist composition in which the edge roughness of the pattern is improved and an excellent resist pattern profile is obtained.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining the constituent material of a positive chemical amplification resist composition, it observed that the objective of this invention is achieved by using two specific acid-decomposable resins, and completed this invention.

That is, the said object is achieved with the following structures.

(A) (A) an alkali-soluble group protected by at least one of the substructures containing alicyclic hydrocarbons represented by the following general formulas (pI) to (pVI), and the content of the monomer component is gel permeation chromatography. A resin which increases the dissolution rate in an alkaline developer by the action of an acid, which is 5% or less of the total pattern area of (GPC), and

Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms. Display.

If at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon group, R ₁₂ to R ₁₆ are each independently a linear or branched alkyl group or alicyclic hydrocarbon having 1 to 4 carbon atoms. Display the flag.

If at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group, and any of R ₁₉ and R ₂₁ represents a straight or branched alkyl group or alicyclic hydrocarbon group having 1 to 4 carbon atoms, then R ₁₇ to R ₂₁ Each hydrogen atom, a straight or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group is represented.

If at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group, R ₂₂ to R ₂₅ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 1 to 4 carbon atoms.)

(C) Positive resist composition containing the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation.

(2) The positive resist composition according to the above (1), wherein the resin (A) is a resin obtained by dropping a reaction solution containing a monomer and a radical initiator into a reaction solvent or a reaction solution containing a monomer and polymerizing the reaction.

(3) The positive resist composition according to the above (1), wherein the resin (A) is a resin obtained by subjecting a reaction solution containing a monomer to a polymerized reaction by dividing a radical initiator over 30 minutes to 8 hours.

(4) The resin according to any one of the above items (1) to (3), wherein the resin (A) is polymerized by heating a reaction solution containing a monomer and a radical initiator, followed by re-adding the radical initiator and heating again. And a positive resist composition obtained by polymerization.

(5) The resin according to any one of (1) to (4), wherein the resin (A) is one of water and alcohols, water / alcohols, water / ethers, and water after completion of the polymerization reaction. A positive resist composition which is a resin obtained by pouring into at least one liquid selected from the group consisting of / ketones, water / amides, water / esters or lactones, and water / nitriles and recovering the powder.

(6) (B) (i) at least one repeating structural unit selected from the repeating structural units represented by the following general formulas (Ia) and (Ib) and the repeating structural unit represented by the following general formula (II) And (ii) have a group decomposed by the action of acid, and (iii) the content of monomer corresponding to the repeating structural unit constituting the resin is 5% or less of the total pattern area of gel permeation chromatography, and the action of acid A positive photoresist composition containing a resin having an increased dissolution rate in an alkaline developer, and (C) an acid generated by irradiation with actinic light and radiation.

In formula (Ia):

R ₁ and R ₂ are each independently a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , an optionally substituted alkyl group or an alkoxy group Or a cyclic hydrocarbon group or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-. Here, R <_5> represents the alkyl group which may have a substituent, a cyclic hydrocarbon group, or the following -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.

A represents a single bond or a divalent linking group.

-Y group;

(In the -Y group, R ₂₁ to R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.)

In formula (Ib):

Z ₂ represents -O- or -N (R ₃ )-, wherein R ₃ represents a hydrogen atom, a hydroxyl group or -OSO ₂ -R ₄ . R ₄ represents an alkyl group, haloalkyl group, cycloalkyl group or camphor residue.

In formula (II):

R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group which may have a substituent.

Z includes two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure which may have a substituent.

(7) In the above (6), Z in the general formula (II) represents an atomic group for forming a pedestrian alicyclic structure which may include two carbon atoms (CC) bonded and may have a substituent. Positive photoresist composition.

(8) The positive photoresist composition according to the above (6), wherein the general formula (II) is the following general formula (II-A) or general formula (II-B).

In formulas (II-A) and (II-B):

R ₁₃ to R ₁₆ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (R ₅ has the same meaning as described above), a group decomposed by the action of an acid, -C (= O ) -XAR ₁₇ or an alkyl or cyclic hydrocarbon group which may have a substituent. In addition, two or more of R ₁₃ to R ₁₆ may be bonded to each other to form a ring. n represents 0 or 1. Here, X and A have the same meanings as above. R ₁₇ is -COOH, -COOR ₅ , -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ (R ₅ , R ₆ are respectively The same meaning as described above) or the -Y group.

(9) In the above (6), the resin of the above (B) is a polymerization reaction by heating a solution containing a monomer and a radical initiator corresponding to the repeating structural unit constituting the resin, and further adding a radical initiator The positive photoresist composition which is a polymer obtained by heating and carrying out a repolymerization reaction.

(10) In the above (6), the resin of the above (B) is water, alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons, and the like after the polymerization reaction A positive photoresist composition, which is a polymer recovered by powdering a polymer by adding it to at least one solvent selected from a solvent group consisting of these mixed solvents.

Hereinafter, the components used in the present invention will be described in detail.

[1] (A) A resin that increases the dissolution rate in an alkaline developer by the action of an acid (referred to as an "acid-decomposable resin")

Hereinafter, each component of the acid-decomposable resin of the present invention will be described.

In general formula (pI)-(pVI), the alkyl group in R <_12> -R <_25> may be either unsubstituted or substituted, and represents the linear or branched alkyl group which has 1-4 carbon atoms. As this alkyl group, a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group etc. are mentioned, for example.

Further, other substituents of the alkyl group include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group And nitro groups.

The alicyclic hydrocarbon group or the alicyclic hydrocarbon group formed by Z and a carbon atom in R ₁₁ to R ₂₅ may be monocyclic or polycyclic. Specifically, the group which has a C5 or more monocyclo, dicyclo, tricyclo, tetracyclo structure, etc. are mentioned. 6-30 are preferable and, as for the carbon number, 7-25 are especially preferable. Such a resin ring hydrocarbon group may have a substituent.

Below, the structural example of an alicyclic part in an alicyclic hydrocarbon group is shown.

In the present invention, preferred examples of the alicyclic moiety include an admanthyl group, a nordemanthyl group, a decarine residue group, a tricyclodecarine group, a tetracyclododecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, and a cyclo Heptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group, etc. are mentioned. More preferably, they are an admantyl group, a decalin residue group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group.

As a substituent of such an alicyclic hydrocarbon group, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and particularly preferably represents a substituent selected from the group consisting of methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group.

Alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in the said resin, there exist various groups known in the art. Specifically, there are a carboxylic acid group, a sulfonic acid group, a phenol group, a thiol group and the like, and among these, a carboxylic acid group and a sulfonic acid group are preferable.

In the said resin, what is preferable as alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) is group represented by the following general formula (pVII)-(pXI).

Here, R ₁₁ to R ₂₅ and Z are as defined above, respectively.

In the said resin, the repeating unit represented by the following general formula (pA) is good as a repeating unit which retains the alkali-soluble group protected by the structure represented by general formula (pI)-(pVI).

Here, R represents a hydrogen atom, a halogen atom or a substituent having 1 to 4 carbon atoms or an unsubstituted linear or branched alkyl group. A plurality of Rs may be the same or different, respectively. A is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a combination of two or more groups selected from the group consisting of urea groups Is displayed.

Ra represents the group in any one of said formula (pI)-(pVI).

Hereinafter, the specific example of the monomer corresponding to the repeating unit represented by general formula (pA) is shown.

In the said resin, you may contain other repeating units other than the repeating unit which retains the alkali-soluble group protected by the structure represented by said general formula (pI)-(pVI).

Preferable as such other repeating units are repeating units represented by the following general formula (AI).

R has the same meaning as described above. B represents a halogen atom, a cyano group, a group decomposed by the action of an acid, -C (= O) -YAR _C9 or -COOR _C11 .

Y is a divalent bonding group selected from oxygen atom, sulfur atom, -NH-, -NHSO2-, -NHSO2NH-,

R _C9 : -COOH, -COOR _C10 (R _C10 has the same meaning as R _C11 and represents the following lactone structure), -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-R _C11 , -CO-NH-SO ₂ -R _C11 or the following lactone structure is represented.

R _C11 : an alkyl group which may have a substituent, a cyclic hydrocarbon group which may have a substituent,

A: single or combination of two or more selected from the group consisting of a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, or a urea group do.

Ra to Re each independently represent a hydrogen atom or a C1-4 straight or branched alkyl group which may have a substituent. m and n each independently represent an integer of 0 to 3, and m + n is 2 or more and 6 or less.

The group decomposed by the action of the acid is preferably a group represented by -C (= 0) -X ₁ -R 0. Here, as R0, tertiary alkyl groups, such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, etc. And alkoxymethyl groups such as 1-alkoxyethyl group, 1-methoxymethyl group, and 1-ethoxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl group, and 3-oxocyclohexyl group. X ₁ represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , -NHSO ₂ NH-, but an oxygen atom is preferable.

As said alkyl group, a C1-C10 linear or branched alkyl group is preferable, More preferably, a C1-C6 linear or branched alkyl group is the most preferable, A methyl group, an ethyl group, a propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the cyclic hydrocarbon group include a cyclic alkyl group and a piercing hydrocarbon, and include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an admantyl group, a boronyl group, an isoboroyl group, a tricyclodecanyl group, a dicyclopentenyl group, Novonane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclo dodecanyl group, etc. are mentioned.

Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

As said alkyl group, other substituents of a cyclic alkyl group and an alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As an alkoxy group, although there exist some C1-C4, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, an acyl group includes a formyl group, an acetyl group, etc., As an acyloxy group, an acetoxy group is mentioned.

Examples of the alkylene group and substituted alkylene group of A in the formulas (AI) and (pA) include the groups shown below.

[C (Rf) (Rg)] r-

Food,

Rf, Rg: represents a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group or an alkoxy group, both of which may be the same or different, and the alkyl group may be a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group. Preferred, with particular preference being given to substituents selected from the group consisting of methyl, ethyl, propyl, isopropyl groups. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned. As the alkoxy group, there are ones having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. r represents the integer of 1-10.

In the above, the halogen atom includes chlorine atom, bromine atom, fluorine atom, iodine atom and the like.

As said B, group represented by an acid-decomposable group and -COOR _C9 (lactone structure) is preferable.

In the present invention, the acid-decomposable resin is an acid other than an alkali-soluble group protected by a structure represented by general formulas (pI) to (pVI) in copolymerized components such as repeating units represented by general formula (AI) as described above. It is preferable to contain a decomposable group. As such a usable acid-decomposable group, the group represented by -C (= O) -O-R0 is preferable.

Moreover, as a preferable example of the structure represented by the said general formula (pI)-(pVI), the said specific example (5)-(8) which is 2-alkyl- 2-ademantan and an acid-decomposable alicyclic monomer are especially preferable. Here, as an alkyl group, it is preferable that it is C1-C4.

It is preferable that acid-decomposable resin further contains the repeating structural unit represented by the following general formula (III-a)-(III-d). This improves the problem due to the hydrophobicity of the resist composition.

R <_1> is synonymous with R of the said general formula (pA) in said Formula (III-a)-(III-d). R ₅ to R ₁₂ each independently represent a hydrogen atom or an alkyl group which may have a substituent. R represents an alkyl group, a cyclic alkyl group, an aryl group or an aralkyl group which may have a hydrogen atom or a substituent. m represents the integer of 1-10.

X is selected from the group consisting of an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, and a urea group which may have a single bond or a substituent A bivalent group which is not decomposed by the action of an acid, alone or in combination of two or more of these groups is represented.

Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group, or a divalent group combining these. R <_13> represents a single bond, an alkylene group, an arylene group, or the bivalent group which combined these. R <_15> represents an alkylene group, an arylene group, or the bivalent group which combined these. R <_14> represents the alkyl group, cyclic alkyl group, aryl group, or aralkyl group which may have a substituent. R <_16> represents the alkyl group, cyclic alkyl group, alkenyl group, aryl group, or aralkyl group which may have a hydrogen atom or a substituent.

A represents either of the functional groups shown below.

In general formula (III-a)-(III-d), the alkyl group of R <_3> -R <_10> , R, R <_12> , and R <_14> may be any of the linear and branched phase which may have a substituent. As said linear or branched alkyl group, it is preferable that it is C1-C12, and it is more preferable that it is C1-C10, Specifically, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group , sec-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, nonyl or decyl groups are most preferred.

The cyclic alkyl group represented by R, R ₁₂ and R ₁₄ has 3 to 30 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an admantyl group, a norbornyl group, a boronyl group and a tri Cyclodecanyl group, dicyclopentenyl group, norbornaneepoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group and steroid residues.

The aryl group represented by R, R ₁₂ and R ₁₄ includes an aryl group having 6 to 20 carbon atoms, which may have a substituent. Specifically, there are phenyl group, toryl group and naphthyl group.

The aralkyl group represented by R, R ₁₂ and R ₁₄ has one having 7 to 20 carbon atoms, which may have a substituent. Specifically, there are benzyl group, phenethyl group and cumyl group.

The alkenyl group represented by R ₁₄ includes an alkenyl group having 2 to 6 carbon atoms, and detailed examples thereof include vinyl group, propenyl group, aryl group, butenyl group, pentenyl group, hexenyl group, cyclopentenyl group and cyclohexenyl Group, 3-oxocyclohexenyl group, 3-oxocyclopentenyl group, and 3-oxoindenyl group. Among these, the cyclic alkenyl group may contain an oxygen atom.

Examples of the linking group X include an alkylene group, a cyclic alkylene group, an arylene group or an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group and a urea group which may have a substituent. However, there are divalent groups in which two or more of these groups are combined and are not decomposed by the action of an acid.

Z represents a single bond, an ether group, an ester group, an amide group, an alkylene group or a divalent group in which these are combined.

R ₁₁ represents a single bond, an alkylene group, an arylene group or a divalent group in which these are combined.

R ₁₃ represents an alkylene group, an arylene group or a divalent group in which these are combined.

In X, R ₁₁ and R ₁₃ , there are some arylene groups having 6 to 10 carbon atoms, which may have a substituent. Specifically, there are phenylene group, toylene group and naphthylene group.

The cyclic alkylene group of X includes the above-described cyclic alkyl group which is divalent.

The alkylene group represented by X, Z, R ₁₁ and R ₁₃ has the same meaning as A in the general formula (pA).

Specific examples of the connector X are shown below, but are not limited to these.

Further substituents of the alkyl group, cyclic alkyl group, alkenyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group and arylene group include carboxyl group, acyloxy group, cyano group, alkyl group, substituted alkyl group, halogen atom, hydroxyl group, alkoxy Groups, acetylamide groups, alkoxycarbonyl groups and acyl groups.

Here, the alkyl group includes a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, cyclopropyl group, cyclobutyl group and cyclopentyl group. Substituents of the substituted alkyl group include a hydroxyl group, a halogen atom and an alkoxy group. The alkoxy group includes an alkoxy group having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, the acyloxy group has an acetoxy group, and the halogen atom has chlorine, bromine, fluorine and iodine There is an atom.

Hereinafter, although the structure of the side chain in which X was excluded as a specific example of the side chain structure of general formula (III-b) is shown below, this invention is not limited to this at all.

Hereinafter, although the detailed example of the monomer corresponding to the repeating structural unit represented by general formula (III-c) is shown, this invention is not limited to this at all.

Hereinafter, although the specific example of the repeating structural unit represented by general formula (III-d) is shown, this invention is not limited to this at all.

In general formula (III-b), as R <_3> -R <_10> , a hydrogen atom and a methyl group are preferable. R is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m is preferably an integer of 1 to 6 carbon atoms.

In formula (III-c), R ₁₁ is preferably a single bond, an alkylene group such as methylene group, ethylene group, propylene group and butylene group, and R ₁₂ is an alkyl group having 1 to 10 carbon atoms, such as methyl group and ethyl group, cyclopropyl group Preference is given to cyclic alkyl groups such as cyclohexyl group and camphorzan group, naphthyl group and naphthylmethyl group. Z is preferably a single bond, an ether bond, an ester bond, an alkylene group having 1 to 6 carbon atoms, or a combination thereof, and more preferably a single bond or an ester bond.

In formula (III-d), R ₁₃ is preferably an alkylene group having 1 to 4 carbon atoms, and R ₁₄ is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, neopentyl group and octyl group which may have a substituent. Alkyl group having 1 to 8 carbon atoms, cyclohexyl group, admantyl group, norbornyl group, boronyl group, isoboroyl group, menthyl group, morpholino group, 4-oxocyclohexyl group, phenyl group which may have a substituent, tolu Diary, menthyl, naphthyl and camphor groups are preferred. As another substituent of this group, a halogen atom such as a fluorine atom or an alkoxy group having 1 to 4 carbon atoms is preferable.

Also in general formula (III-a)-(III-d), the repeating structural unit represented by general formula (III-b) and (III-d) is preferable.

The acid-decomposable resin (A) is, in addition to the repeating structural unit, for the purpose of controlling dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are generally necessary properties of the resist, It may contain various repeating structural units.

Although the repeating structural unit corresponding to the following monomer is mentioned as such a repeating structural unit, It is not limited to these.

This results in the performance required for acid-decomposable resins, in particular

(1) solubility in coating solvents,

(2) Film forming property (glass transition point)

(3) alkali developability

(4) Membrane loss (choose hydrophilic, alkali soluble group)

(5) Adhesion to Substrate of Unexposed Part

(6) dry etching resistance

It becomes possible to adjust etc. to a minute part.

Examples of such monomers include addition polymerizable unsaturated bonds selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylic acid amides, aryl compounds, vinyl ethers, vinyl esters, and the like. The compound which a dog holds is mentioned.

Specifically, the following monomers can be illustrated.

Acrylic esters (preferably the number of carbon atoms of an alkyl group is 1-10):

Methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethyl hexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-diethyl hydrate Hydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimetholpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, perfuryl acrylate, tetrahydroperfuryl acrylate Etc.

Methacrylic acid esters (the alkyl group preferably has 1 to 10 carbon atoms):

Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, crawlbenzyl methacrylate, octyl methacrylate Acrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimetholpropane mono Methacrylate, pentaerythritol monomethacrylate, perfuryl methacrylate, tetrahydrofurfuryl methacrylate and the like.

Acrylamides:

Acrylamide, N-alkylacrylamide, (The alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, t-butyl, heptyl group, octyl group, cyclohexyl group, hydroxy N, N-dialkylacrylamide (The alkyl group includes 1-10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, cyclohexyl group, etc.) N-hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide, and the like.

Methacrylamides:

Methacrylamide, N-alkyl methacrylamide (as alkyl groups having 1 to 10 carbon atoms, for example, methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, cyclohexyl group, etc.), N, N-dialkyl methacrylamide (alkyl groups include ethyl group, propyl group, butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide, and the like.

Aryl Compounds:

Aryl esters (for example, aryl acetate, caprylic acid, capryl aryl, aryl laurate, aryl palmitate, aryl stearic acid, aryl benzoate, aryl acetic acid, aryl lactate, etc.), aryloxyethanol and the like.

Vinyl ethers:

Alkyl vinyl ether (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, crawl ethyl vinyl ether, 1-methyl-2,2- Dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydroper Furyl vinyl ether and the like.

Vinyl esters:

Vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl crawl acetate, vinyl dicro acetate, vinyl methoxy acetate, vinyl butoxy acetate, vinyl acetate acetate, vinyl lactate , Vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like.

Itaconic acid alkyls:

Methyl itacate, diethyl itaconic acid, dibutyl itaconic acid, and the like.

Dialkyl esters or monoalkyl esters of fumaric acid; dibutyl fumarate and the like

Other crotonic acid, itaconic acid, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile, maleilonitrile and the like.

In addition, as long as it is an addition-polymerizable unsaturated compound which can copolymerize with the monomer corresponding to the said various repeating structural unit, you may copolymerize.

In acid-decomposable resins, the molar ratio of each repeating structural unit is appropriately set to adjust the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, and the resolution, heat resistance, sensitivity, and the like, which are general necessary capabilities of the resist. do.

As for content of the repeating structural unit containing alkali-soluble group protected by the structure represented by general formula (pI)-(pVI) in acid-decomposable resin, 30-70 mol% is preferable in all the repeating structural units, More preferably, It is 35-65 mol%, Most preferably, it is 40-60 mol%.

As for content of the repeating structural unit represented by general formula (III-a)-(III-d) in acid-decomposable resin, 0-20 mol% is preferable in all the repeating structural units, More preferably, it is 0-18 mol% Most preferably, it is 0-16 mol%.

In acid-decomposable resin, content of the repeating structural unit containing acid-decomposable groups other than the repeating structural unit containing alkali-soluble group protected by the structure represented by said general formula (pI)-(pVI) is 0 in all the repeating structural units. 20 mol% is preferable, More preferably, it is 0-18 mol%, Most preferably, it is 0-16 mol%.

The content of the repeating structural unit containing the lactone structure in the acid-decomposable resin is preferably 20 to 70 mol%, more preferably 25 to 65 mol%, most preferably 30 to 60 mol% of all the repeating structural units. .

The content in the resin of the repeating structural unit may also be appropriately set according to the performance of the desired resist, based on the monomer of the other copolymerization component, but generally protected by the structures represented by the above general formulas (pI) to (pVI). It is preferable that it is 99 mol% or less with respect to the total mole number which totaled the repeating structural unit containing an alkali-soluble group, More preferably, it is 90 mol% or less, Most preferably, it is 80 mol%.

As for the acid-decomposable resin used for this invention, content of a monomer component is 5% or less of the total pattern area of gel permeation chromatography (GPC), Preferably it is 0.01 to 4%, More preferably, it is 0.1 to 3%. Here, for example, shodex system-11, which is manufactured by Digestion Electric Co., Ltd., can be used.

As GPC, by making the content of the monomer contained in an acid-decomposable resin into the said content, a high sensitivity, the outstanding edge roughness, and a pattern profile are obtained in a photoresist composition.

The acid-decomposable resin used in the present invention can be synthesized by a general method (for example, radical polymerization), but it is preferable that the specific monomer amount is one or more of the following means (i) to (iv). It is carried out by synthesizing or recovering using.

(i) A reaction solution containing each monomer and a radical initiator is added dropwise to a reaction solvent or a reaction solution containing a monomer to cause a polymerization reaction.

(ii) The reaction solution containing each monomer and the radical initiator was polymerized by split injection of a radical initiator over 30 minutes to 8 hours.

(iii) After the reaction solution containing each monomer and the radical initiator is heated and polymerized, the radical initiator is added thereto, reheated and polymerized.

(iv) After completion of the polymerization reaction, the reaction solution is water, one or more of alcohols, water / alcohols, water / ethers, water / ketones, water / amides, water / esters or lactones, and water / nitriles. It is put into at least one liquid selected from the group consisting of, and recovered in powder.

In the present invention, it is particularly preferable to combine one of the means of i) and iii), one of ii) and iii), or a combination of these and iv).

A specific synthesis method is described below.

The reacted monomer is added to the reaction solvent at the same time as the initiator, and a portion of the reaction solvent or monomer heated to a desired temperature under a nitrogen atmosphere is added to the reaction solvent to slowly dropwise add the solution (the method of (i) above). )

The reacted monomer is added to the reaction solvent, homogenized, heated and stirred under a nitrogen atmosphere to a desired temperature, followed by partial addition of a radical initiator at a predetermined time for polymerization (the method of (ii) above), and

The reacted monomer is added to the reaction solvent to make it uniform, heated and stirred under a nitrogen atmosphere to a desired temperature, and then a radical initiator is added in a batch to polymerize, and then the initiator is added again (the method of (iii) above). Or a combination of the methods.

Preferred is the dropping method of (i). By selecting the dropping method of (i), all the properties of the resist that give priority to resolution and edge roughness, which are the effects of the present invention, are further improved, even though the specific part is not sure.

In the present invention, the reaction temperature may be appropriately set depending on the type of initiator in the above reactions, but 30 ° C to 180 ° C is generally used. Preferably it is 40 degreeC-160 degreeC, More preferably, it is 50 degreeC-140 degreeC.

The dropping time in the case of employing the dropping method of (i) may be set in various ways depending on the reaction temperature, the type of initiator, and the type of the monomer reacted, but is 30 minutes to 8 hours. Preferably it is 45 minutes-6 hours, More preferably, it is 1 hour-5 hours.

In the method of (i), when dropping into a solution containing a monomer, the content of the monomer in the dropping solution is preferably 30 mol% or more relative to the total amount of the monomer in (dropping solution + dropping solution), more Preferably it is 50 mol% or more, Most preferably, it is 70 mol% or more.

Initiation time of the initiator in the case of employing the method of (ii) can be set in various ways depending on the reaction temperature, the type of initiator, and the reacted monomer, but it is 30 minutes to 8 hours. Preferably they are 45 minutes-6 hours, Most preferably, they are 1 hour-5 hours. In the method of (ii), the injection interval of the initiator is preferably 10 minutes to 3 hours, more preferably 20 minutes to 2 hours 30 minutes, and most preferably 30 minutes to 2 hours. Moreover, as for the said input frequency, 2 times-20 times are preferable, 3 times-15 times are more preferable, Most preferably, they are 4 times-10 times.

In the case of the method (ii) or (iii), after completion of the initiator addition, the mixture is heated and stirred at a desired temperature under a nitrogen atmosphere for a predetermined time. In addition, in the case of the dropping method of (i), the mixture is heated and stirred at a desired temperature under a nitrogen atmosphere for a predetermined time after completion of dropping. The heating time varies depending on the reaction temperature and the type of initiator, but generally within 10 hours. Preferably it is within 8 hours, More preferably, it is within 6 hours.

In any case, the method of adding a 2nd initiator after this heating stirring for a certain time is preferable. By using the addition of the initiator, it is not sure to the specific part, but as a result, the sensitivity, resolution and edge roughness are improved. After adding the initiator, the mixture is heated and stirred for a predetermined time. Moreover, you may raise reaction temperature after adding an initiator.

The solvent used in the reaction can be used as long as it is not various solvents that dissolve the monomer species used and inhibit polymerization (for example, no polymerization, for example, nitrobenzene, chain transfer, for example, mercapto compounds). . For example, there are alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons and mixtures thereof. Alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol. Examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and 1,3-dioxane. Acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone are mentioned as ketones. Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide. Ester and lactones include ethyl acetate, methyl acetate, isobutyl acetate and γ-butyrolactone. Examples of nitriles include acetonitrile, propionitrile and butyronitrile.

Preferred solvents include 1-methoxy-2-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 1,3-dioxane And methyl ethyl ketone, N, N-dimethylformamide, N, N-dimethylacetamide, γ-butyrolactone and acetonitrile.

Mixed solvent systems include alcohols and ethers, alcohols and ketones, alcohols and amides, alcohols and esters and lactones, ethers, ethers and ketones, ethers and amides, ethers and esters and lactones, Ethers and nitriles, ketones and amides, ketones and esters and lactones, ketones and nitriles, amides and esters and lactones, amides and nitriles, esters and lactones and nitriles. .

Preferred mixed solvent systems include 1-methoxy-2-propanol and tetrahydrofuran, 1-methoxy-2-propanol and 1,4-dioxane, 1-methoxy-2-propanol and 1,3-dioxolane , 1-methoxy-2-propanol and 1,3-dioxane, 1-methoxy-2-propanol and methyl ethyl ketone, 1-methoxy-2-propanol and N, N-dimethylformamide, 1-methoxy Methoxy-2-propanol and N, N-dimethylacetamide, 1-methoxy-2-propanol and γ-butyrolactone, ethylene glycol monomethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether and 1,4-di Oxane, ethylene glycol monomethyl ether, 1,3-dioxolane, ethylene glycol monomethyl ether, 1,3-dioxane, ethylene glycol monomethyl ether, methyl ethyl ketone, ethylene glycol monomethyl ether, N, N-dimethyl Formamide, ethylene glycol monomethyl ether and N, N-dimethylacetamide, ethylene glycol monomethyl ether, γ-butyrolactone, and ethylene glycol mono Tyl ether, tetrahydrofuran, ethylene glycol monoethyl ether, 1,4-dioxane, ethylene glycol monoethyl ether, 1,3-dioxolane, ethylene glycol monoethyl ether, 1,3-dioxane, ethylene glycol mono Ethyl ether, methyl ethyl ketone, ethylene glycol monoethyl ether, N, N-dimethylformamide, ethylene glycol monoethyl ether, N, N-dimethylacetamide, ethylene glycol monoethyl ether, γ-butyrolactone, tetrahydrofuran And 1,4-dioxane, tetrahydrofuran and 1,3-dioxolane, tetrahydrofuran and methyl ethyl ketone, tetrahydrofuran and N, N-dimethylformamide, tetrahydrofuran and N, N-dimethylacet Amides, tetrahydrofuran and γ-butyrolactone, tetrahydrofuran and acetonitrile, methyl ethyl ketone and N, N-dimethylformamide, methyl ethyl ketone and N, N-dimethylacetamide, methyl ethyl ketone and γ-buty Lolacton, Me Ethyl ketone and acetonitrile, N, N-dimethylformamide and γ-butyrolactone, N, N-dimethylacetamide and γ-butyrolactone, N, N-dimethylformamide and acetonitrile, N, N-dimethyl Acetamide and acetonitrile, γ-butyrolactone and acetonitrile.

The amount of the reaction solvent varies depending on the target molecular weight, the monomer used, and the type of initiator used, but considering the monomer and solvent solution, the monomer concentration is generally 12% by weight to 30% by weight, preferably 14% by weight to 28%. It is weight% or more, More preferably, it is 16 weight%-26 weight%.

In addition, in this invention, what is shown below is a radical initiator which can be used for a polymerization reaction.

As a radical initiator, what is generally used, such as a peroxide or an azo initiator, can be used. Preferred are azo initiators. Examples of azo initiators include 2,2-azobis (4-methoxy-2,4-dimethylbareronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azo Bis (2,4-dimethylbareronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'- Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-2-propenylpropionamidine) dihydrochloride, 2,2'-azo Bis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2-methyl-N- [1-1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, dimethyl-2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'- Azobis (2- (hydroxymethyl) propionitrile).

Preferred radical initiators include 2,2'-azobis (2,4-dimethylbareronitrile), 2,2'-azobisisobutyronitrile and 2,2'-azobis (2-methylbutyronitrile ), 1,1'-azobis (cyclohexane-1-carbonitrile), dimethyl2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanobareric acid) ), 2,2'-azobis (2-hydroxymethyl) propionitrile).

In the present invention, the polymer (resin) obtained after the polymerization reaction as described above can be recovered by the reprecipitation method. That is, after completion | finish of superposition | polymerization, a polymerization reaction liquid is thrown into a reprecipitating liquid and the target resin is collect | recovered in powder.

Examples of the reprecipitation liquid include alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons, and mixtures thereof. Alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol. Examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and 1,3-dioxane. Examples of the ketones include acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone. Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide. . Ester and lactones include ethyl acetate, methyl acetate, isobutyl acetate and γ-butyrolactone. Examples of nitriles include acetonitrile, propionitrile and butyronitrile.

Examples of the mixed liquid system include mixed liquid systems between alcohols, mixed liquid systems between hydrocarbons, hydrocarbons / alcohols, hydrocarbons / ethers, hydrocarbons / ketones, hydrocarbons / esters, and lactones.

Specifically, methanol and ethanol, methanol and propanol, methanol and isopropanol, methanol and butanol, ethylene glycol and methanol, ethylene glycol and propanol, ethylene glycol and isopropanol, ethylene glycol and butanol, and 1-methoxy-2-propanol And ethanol, 1-methoxy-2-propanol and propanol, 1-methoxy-2-propanol and isopropanol, 1-methoxy-2-propanol and butanol, water and methanol, water and ethanol, water and propanol, water and Isopropanol, water and butanol, water and ethylene glycol, water and propylene glycol, water and 1-methoxy-2-propanol, water and tetrahydrofuran, water and acetone, water and methyl ethyl ketone, water and N, N-dimethyl Formamide, water and N, N-dimethylacetamide, water and γ-butyrolactone, water and acetonitrile. The mixing ratio of the mixed liquid system is 20/1 to 1/120.

Preferred reprecipitates are at least one selected from the group consisting of water or alcohols, water / alcohols, water / ethers, water / ketones, water / amides, water / esters or lactones, water / nitriles It is liquid.

Preferred reprecipitates include water, methanol, isopropanol, water and methanol, water and ethanol, water and propanol, water and isopropanol, water and butanol, water and ethylene glycol, water and propylene glycol, water and 1-methoxy-2-propanol Water and tetrahydrofuran, water and acetone, water and methyl ethyl ketone, water and N, N-dimethylformamide, water and N, N-dimethylacetamide, water and γ-butyrolactone, water and acetonitrile . Particularly preferred are methanol and isopropanol, water and methanol, water and ethanol, water and propanol, water and isopropanol, water and ethylene glycol, water and 1-methoxy-2-propanol, water and tetrahydrofuran, water and acetone, Water and methyl ethyl ketone.

Reprecipitation with a hydrocarbon solvent represented by reprecipitating hexane or butane described in Japanese Patent Application Laid-Open Nos. 9-73173, 10-207069, and 10-274852 is very dangerous, such as generating a constant voltage charging of the positive electrode, It is not good because of difficulty of workability.

Furthermore, the repetition of the reprecipitation as described in, for example, Japanese Patent Laid-Open No. 10-301285 unnecessarily increases the waste liquid, does not improve the working efficiency, and also worsens the edge roughness. In the present invention, the number of reprecipitations is preferably one to three times, and preferably one time.

The amount of the reprecipitation liquid is selected and set depending on the amount of solvent used in the polymerization, the kind and the type of the reprecipitation liquid, but it is 3 to 100 times the polymerization solution. Preferably it is 4 times-50 times, More preferably, it is 5 times-30 times. When this amount is small, it will become difficult to separate from the powder to collect | recover, and work efficiency will worsen. In many cases, it is undesirable in terms of cost, such as an increase in waste liquid.

As described above, the molecular weight of the acid-decomposable resin is a weight average (Mw: polystyrene equivalent value by the GPC method), preferably 3,000 to 100,000, more preferably 4,000 to 70,000, and most preferably in the range of 5,000 to 50,000. . When molecular weight increases, heat resistance etc. improve, but since developability etc. fall, these balances are adjusted in an appropriate range.

In the positive resist composition of the present invention, the blending amount of the acid-decomposable resin in the entire resist composition is preferably 40 to 99.99% by weight in total solids, more preferably 50 to 99.97% by weight.

Below, the preferable specific example which combined the repeating structural unit of acid-decomposable resin which is (A) component is shown.

[2] (B) A resin in which the dissolution rate in an alkaline developer increases due to the action of an acid (called an acid-decomposable resin).

Hereinafter, each component of the acid-decomposable resin of this invention is demonstrated.

In the general formula (Ia), R ₁ and R ₂ are each individually a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , an alkyl group, an alkoxy group or a cyclic hydrocarbon group which may be substituted, or the above-Y group is represented. Here, R <_5> represents the alkyl group which may have a substituent, a cyclic hydrocarbon group, or the said -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.

In the -Y group, R ₂₁ to R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent, and a and b represent 1 or 2.

X represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , -NHSO ₂ -NH-.

A represents a single bond or a divalent linking group.

In Formula (Ib), Z ₂ represents -O- or -N (R ₃ )-. Here, R ₃ represents a hydrogen atom, a hydroxyl group or -OSO ₂ -R ₄ . R ₄ represents an alkyl group, haloalkyl group, cycloalkyl group or camphor residue.

As said alkyl group in said R <_1> , R <_2> , R <_4> , R <_5> , R <_6> -R <_21> -R <_30> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is C1-C6 Linear or branched alkyl groups, most preferred are methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

As said cyclic hydrocarbon group in said R <_1> , R <_2> , R <_5> , and R <_6> , a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an admantyl group, 2-methyl- 2-ademanthyl group, a norbornyl group, a boroyl group , Isoboroyl group, tricyclodecanyl group, dicyclopentenyl group, norbornane epoxy group, menthyl group, isomentyl group, neomentyl group, tetracyclododecanyl group and the like.

As said alkoxy group in said R <_1> , R <_2> , C1-C4 things, such as a methoxy group, an ethoxy group, a propoxy group, butoxy group, are mentioned.

Examples of the haloalkyl group in R ₄ include trifluoromethyl group, nonafluorobutyl group, pentadecafluorooctyl group, trichloromethyl group and the like. A cyclopentyl group, a cyclohexyl group, a cyclooctyl group etc. are mentioned as a cycloalkyl group in said R <_4> .

As other substituents, such as an alkyl group, a cyclic hydrocarbon group, and an alkoxy group, a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, an acyloxy group, etc. are mentioned. Examples of the halogen atom include chlorine atom, fluorine atom, bromine atom and iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group, butoxy group, acyl group include formyl group and acetyl group, and acyloxy group include acetoxy group and the like. Can be mentioned.

As the divalent linking group of A in the general formulas (Ia) and (Ib), an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group, a sulfonamide group, a urethane group, There may be a single or two or more groups selected from the group consisting of urea groups and the like.

In said A, group represented by a following formula is mentioned as an alkylene group and substituted alkylene group.

[C (R ₂ ) (R _b )] r-

In the formula, R ₂ , R _b represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, and both may be the same or different. The alkyl group is preferably a lower alkyl group such as methyl group, ethyl group, propyl group, isopropyl group or butyl group, and more preferably is selected from methyl group, ethyl group, propyl group and isopropyl group. As a substituent of a substituted alkyl group, a hydroxyl group, a halogen atom, an alkoxy group, etc. are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc. are mentioned. r represents the integer of 1-10.

Specific examples of the repeating structural unit represented by the general formula (Ia) include the following [I-1] to [I-65], but the present invention is not limited to these specific examples.

Specific examples of the repeating structural unit represented by the general formula (Ib) include the following [I'-1] to [I'-7], but the present invention is not limited thereto.

In the general formula (II), R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a cyano group, a halogen atom, or an alkyl group which may have a substituent. Z represents an atomic group for forming an alicyclic structure which may have a substituent including two bonded carbon atoms (CC).

Examples of the halogen atom in R ₁₁ and R ₁₂ include a chlorine atom, a fluorine atom, a bromine atom, and an iodine atom.

As said alkyl group in said R <_11> , R <_12> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, Most preferable is a methyl group, an ethyl group, and a propyl group , Isopropyl group, n-butyl group, isobutyl group, sec-butyl, t-butyl group.

Examples of other substituents in the alkyl group in R ₁₁ and R ₁₂ include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. Examples of the halogen atom include chlorine atom, fluorine atom, bromine atom and iodine atom. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group. A formyl group, an acetyl group, etc. are mentioned. And as an acyloxy group, there are an acetoxy group.

The atomic group for forming the alicyclic structure of Z is an atomic group in which a repeating structural unit of an alicyclic hydrocarbon which may have a substituent is formed in the resin, and among these, Confucianism forming a repeating structural unit of an alicyclic type alicyclic hydrocarbon. Atom groups for forming an alicyclic structure are preferable.

As a skeleton of the formed alicyclic hydrocarbon, what is represented by the following structure is mentioned.

As the skeleton of the preferred cyclic alicyclic hydrocarbon, (5), (6), (7), (9), (10), (13), (14), (15) and (23) in the above structure. , (28), (36), (37), (42), and (47).

As the skeleton of the alicyclic hydrocarbon, one having a substituent may be used. As such a substituent, R <_13> -R <_16> in the said general formula (II-A) or (II-B) is mentioned.

Among the repeating structural units having the above-mentioned alicyclic hydrocarbon, the repeating structural unit represented by the general formula (II-A) or (II-B) is more preferable.

In formula (II-A) or (II-B), each of R ₁₃ to R ₁₆ is a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (even if R ₅ has a substituent) May be an alkyl group, a cyclic hydrocarbon group or the same -Y group as in the general formula (I)), a group decomposed by the action of an acid, an -C (= O) -XAR ₁₇ , or an alkyl group which may have a substituent Or a cyclic hydrocarbon group. n represents 0 or 1. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO _2- , or -NHSO ₂ NH-. R ₁₇ is -COOH, -COOR ₅ , -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ (R ₅ , R ₆ is The same meaning as the above) or -Y group of the general formula (Ia). A represents a single bond or a divalent linking group.

In the acid-decomposable resin used in the present invention, the acid-decomposable group may be included in the above -C (= O) -X-AR ₁ , -C (= O) -XAR ₂ , and a substituent of Z in the general formula (II). It may be included as.

The structure of the acid-decomposable group is represented by -C (= 0) -X ₁ -R ₀ .

In formula, R <_0> is tertiary alkyl groups, such as a t-butyl group and a t-acyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1-isobutoxyethyl group, 1-cyclohexyloxyethyl group, etc. Alkoxymethyl groups such as 1-alkoxyethyl group, 1-methoxymethyl group, 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group , 2-methyl-2-ademantyl group, mevalonic lactone residue, 2- (γ-butyrolactylylcarbonyl) -2-propyl group, and the like. X ₁ has the same meaning as X.

Examples of the halogen atom in R ₁₃ to R ₁₆ include a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

As said alkyl group in said R <_13> -R <_16> , a C1-C10 linear or branched alkyl group is preferable, More preferably, it is a C1-C6 linear or branched alkyl group, Most preferable is a methyl group, an ethyl group, and propyl Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group.

Examples of the cyclic hydrocarbon group in R ₁₃ to R ₁₆ include a cyclic alkyl group and a pedophilic hydrocarbon, and include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an admantyl group, a 2-methyl-2-adamantyl group, Norbornyl group, a boronyl group, an isobornyl group, a tricyclo decanyl group, a dicyclopentenyl group, a norbornane epoxy group, a menthyl group, an isomentyl group, a neomentyl group, a tetracyclo dodecanyl group, etc. are mentioned.

Examples of the ring formed by bonding two or more of R ₁₃ to R ₁₆ to each other include a ring having 5 to 12 carbon atoms such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.

Examples of the alkoxy group in R ₁₇ include one having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Examples of other substituents in the alkyl group, cyclic hydrocarbon group, and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group, and an acyloxy group. As a halogen atom, a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, etc. are mentioned. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as methoxy group, ethoxy group, propoxy group and butoxy group, and acyl group include formyl group and acetyl group, and acyloxy group includes acetoxy group. .

As said divalent linking group of A, it is synonymous with the divalent linking group of A in the said general formula (Ia), and is a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group Or a combination of two or more groups selected from the group consisting of a sulfonamide group, a urethane group, and a urea group.

As said alkylene group and substituted alkylene group in said A, the thing similar to the thing of the bivalent coupling group of A in the said General formula (Ia) is mentioned.

In the acid-decomposable resin used in the present invention, the group decomposed by the action of an acid is represented by a repeating structural unit represented by general formula (Ia), a repeating structural unit represented by general formula (Ib), and general formula (II). It may be contained in one or more repeating structural unit of the repeating structural unit, and the repeating structural unit of the following copolymerization component.

In the above general formula (II-A) or (II-B), the various substituents of R ₁₃ to R _{16 form} a cyclic cyclic alicyclic structure without an atom group for forming an alicyclic structure in the general formula (II). It consists of a substituent of the atomic group Z to make.

Specific examples of the repeating structural unit represented by the above (II-A) or (II-B) include the following [II-1] to [II-166], but the present invention is not limited thereto.

The acid-decomposable resin used in the present invention is a unit of any one of the repeating structural units represented by General Formula (Ia) and General Formula (Ib), and General Formula (II) (General Formula (II-A) or (II) In addition to including one or more repeating structural units each of which is represented by (B)), developability, heat resistance and sensitivity, which are general requirements for dry etching resistance, standard developer aptitude, substrate adhesion, resist profile and resist It may be a copolymer containing repeating structural units of various monomers for the purpose of controlling such as.

As a preferable copolymerization component, the repeating structural unit represented by the following general formula (IV ') and (V') is mentioned.

Wherein Z represents an oxygen atom, -NH-, -N (-R ₅₀ )-, -N (-OSO ₂ -R ₅₀ )-, and R ₅₀ represents the same (substituted) alkyl group as described above, ( Substituted) means a cyclic hydrocarbon group.

Specific examples of the repeating structural unit represented by the general formulas (IV ') and (V') include the following [IV'-9] to [IV'-16], [V'-9] to [V'-16]. Although this is not limited to these specific examples.

The acid-decomposable resin used in the present invention may be copolymerized by providing a repeating structural unit constituting the resin within the range in which the effect of the present invention is effectively obtained, and the following monomers are not limited to the following monomers. .

Thereby, the performance required for the said resin, especially

(1) solubility in coating solvents,

(2) Film forming property (glass transition point)

(3) alkali developability

(4) Membrane loss (choose hydrophilic, alkali soluble group)

(5) Adhesion to Substrate of Unexposed Part

(6) dry etching resistance

It can be adjusted to a minute part.

As such a copolymerization monomer, the addition polymerizable unsaturated bond chosen from acrylic acid ester, methacrylic acid ester, acrylamide, methacrylic acid amide, aryl compound, vinyl ether, vinyl ester, etc. is used, for example. The compound which holds one is mentioned.

Specifically, for example, acrylate esters, which include alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) acrylate (e.g. methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cycloacrylate Hexyl, ethylhexyl acrylate, octyl acrylate, t-octyl acrylate, chloroethyl acrylate, 2-hydroxyethyl acrylate, 2,2-diethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimeth Tyrolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, perfuryl acrylate, tetrahydrofurfuryl acrylate, etc.);

Methacrylic acid esters, for example, alkyl (preferably having 1 to 10 carbon atoms in the alkyl group) methacrylate (for example, methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate) Acrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, crawlbenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate Acrylate, 5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimetholpropane monomethacrylate, pentaerythritol monomethacrylate, perfuryl methacrylate , Tetrahydrofurfuryl methacrylate, and the like);

Acrylamides, for example acrylamide, N-alkyl acrylamide, (alkyl group having 1 to 10 carbon atoms, for example methyl group, ethyl group, propyl group, butyl group, t-butyl, heptyl group, octyl group , Cyclohexyl group, hydroxyethyl group, etc.) N, N-dialkylacrylamide (The alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, Cyclohexyl group, etc.) N-hydroxyethyl-N-methylacrylamide, N-2-acetamideethyl-N-acetylacrylamide, etc .;

Methacrylamides, for example methacrylamide, N-alkyl methacrylamide (as alkyl group having 1 to 10 carbon atoms, for example methyl group, ethyl group, t-butyl group, ethylhexyl group, hydroxyethyl group, Cyclohexyl group and the like), N, N-dialkyl methacrylamide (alkyl groups include ethyl group, propyl group, butyl group and the like), N-hydroxyethyl-N-methylmethacrylamide and the like;

Aryl compounds, such as aryl esters (e.g., aryl acetate, caprylic acid, caprylaryl, aryl laurate, aryl palmitate, aryl stearic acid, benzoate, aryl acetic acid, aryl lactate, etc.) Aryloxyethanol and the like;

Vinyl ethers, for example alkyl vinyl ethers (for example, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxy ethyl vinyl ether, ethoxy ethyl vinyl ether, crawlethyl vinyl ether, 1 -Methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, Benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl barrate, vinyl caproate, vinyl crawl acetate, vinyl dicro acetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetate acetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexyl carboxylate and the like;

Alkyl itaconic acids (for example, methyl itacate, diethyl itaconic acid, dibutyl itaconic acid, etc.);

Acrylic acid, methacrylic acid, cronic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

In the acid-decomposable resin used in the present invention, a repeating structural unit represented by general formula (Ia) and / or general formula (Ib), and general formula (II) (General formula (II-A) or (II-B) The content of the repeating structural unit represented by) is suitably in consideration of dry etching resistance, sensitivity of the desired resist, preventing cracking of the pattern, substrate adhesion, resist profile, and resolution, heat resistance, which are the requirements of general resist. Can be set. In general, in the acid-decomposable resin used in the present invention, the content of the repeating structural unit represented by the general formula (Ia) and / or the general formula (Ib) and the repeating structural unit represented by the general formula (II) are each resin. At least 25 mol% of all monomer repeating structural units are suitable, preferably at least 30 mol%, more preferably at least 35 mol%.

In addition, in the acid-decomposable resin used in the present invention, the content in the resin of the repeating structural unit (General Formula (IV ′) or (V ′)) derived from the above-mentioned preferred copolymer monomer can be set as appropriate for the performance of the desired resist. However, in general, it is preferably 99 mol% or less with respect to the total moles of the sum of the repeating structural units represented by the general formula (Ia) and / or the general formula (Ib) and the repeating structural unit represented by the general formula (II), More preferably, it is 90 mol% or less, and most preferably 80 mol% or less.

Moreover, although content in resin of the repeating structural unit based on the monomer of the said other copolymerization component can also be set suitably with respect to the performance of a desired resist, it is generally represented by general formula (Ia) and / or general formula (Ib). It is preferably at most 99 mol%, more preferably at most 90 mol%, most preferably at most 80 mol%, based on the total moles of the total of the structural units and the repeating structural units represented by the general formula (II). If the amount of the repeating structural unit based on this and other copolymerized monomers exceeds 99 mol%, the effect of the present invention is not sufficiently expressed, which is not preferable.

In addition, in the acid-decomposable resin used in the present invention, the groups decomposed by the action of an acid are the repeating structural units represented by the general formula (Ia) and / or the general formula (Ib) and the repeating structural unit represented by the general formula (II). Although it may contain any of the repeating structural units based on the monomer of a copolymer, and a copolymerization component, content of the repeating structural group containing group decomposed by the action of an acid is 8-60 mol% of all the repeating structural units of resin. Is suitable, Preferably it is 10-55 mol%, Most preferably, it is 12-50 mol%.

In the acid-decomposable resin used in the present invention, the content of the monomer corresponding to the repeating structural unit constituting the acid-decomposable resin is 5% or less of the total pattern area of the gel permeation chromatography (GPC), preferably 0.01 to 4%. More preferably, it is 0.1 to 3%. Here, as an apparatus which can be used for the measurement by GPC, Shodex system-11 which is a product of Fire Hydrant Co., Ltd. is mentioned, for example.

By using the monomer contained in an acid-decomposable resin as the said quantity, a photoresist composition becomes highly sensitive and the pattern profile excellent also in the edge roughness is obtained.

The acid-decomposable resin used in the present invention is copolymerized in the presence of a polymerization catalyst by copolymerizing a monomer suitable for the repeating structural unit represented by the general formula (II) and maleic anhydride with a monomer of the copolymerization component when a copolymerization component is used. The structural unit obtained by the maleic anhydride of the obtained copolymer can be synthesized by ring-opening esterification with alcohols under basic or acidic conditions, or by hydrolysis to convert the resulting carboxylic acid moiety into a desired substituent.

Incidentally, the copolymerization (hereinafter, simply referred to as "polymerization") can be carried out by a general method (for example, by radical polymerization). have.

After the reaction, the monomer is dissolved in the reaction solvent or homogenized in the absence of a solvent, heated and stirred under a nitrogen atmosphere to a desired temperature, and then a batch method, a split addition method or a monomer to add all or partly the radical initiator is added. To a solution in which a part of a reaction solvent or a monomer dissolved in a reaction solvent together with an initiator and heated to a desired temperature under a nitrogen atmosphere is dissolved in the reaction solvent.

Preferable is the partial addition method or the dropping method of the initiator. Even if the details are not clear, by selecting the same method, all the performances of the resist which give priority to the resolution and edge roughness which are the effects of the present invention are improved.

Although reaction temperature is suitably set according to the kind of initiator, 30 degreeC-180 degreeC is common. Preferably it is 40 degreeC-160 degreeC, More preferably, it is 50 degreeC-140 degreeC.

In the case of the split addition method, the interval between adding the initiator is 5 minutes to 6 hours, preferably 10 minutes to 5 hours, and more preferably 15 minutes to 4 hours.

The dropping time in the case of employing the dropping method may be similarly set by the reaction temperature, the type of initiator, and the reacted monomer, but is 30 minutes to 8 hours. Preferably they are 45 minutes-6 hours, More preferably, they are 1 hour-5 hours.

In addition, in the batch method and the split addition method, after the addition of the initiator is completed, the mixture is heated and stirred at a desired temperature under a nitrogen buried for a certain time. In the case of the dropping method, the mixture is heated and stirred at a desired temperature under a nitrogen atmosphere for a predetermined time after the end of the dropping.

The heating time can be set by the reaction temperature and the type of initiator, but usually within 24 hours. Preferably it is within 20 hours, More preferably, it is within 18 hours.

In any case, the method of adding an initiator again after continuing this heating stirring for a predetermined time is preferable.

By adding an initiator, although it cannot be said to the detailed part reliably, as a result, a sensitivity and a resolution improve. After addition of the initiator, heating and stirring are also performed. Moreover, you may raise reaction temperature after adding an initiator.

As a solvent used for reaction, it can be used if it is not a solvent which melt | dissolves the monomer species to be used and inhibits superposition | polymerization (for example, no polymerization, for example, nitrobenzene, chain transfer, for example, mercapto compound). For example, there are alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons and mixtures thereof.

Alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol.

Examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and 1,3-dioxane.

Acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone are mentioned as ketones.

Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

Ester and lactones include ethyl acetate, methyl acetate, isobutyl acetate and γ-butyrolactone. Examples of nitriles include acetonitrile, propionitrile and butyronitrile.

Examples of the hydrocarbons include straight chain such as pentane, hexane, heptane and octane, or branched hydrocarbons, cyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as ketone and xylene.

Preferred solvents are propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, 1,3-dioxane, acetone, methyl ethyl ketone, diethyl ketone And methyl isopropyl ketone, methyl isobutyl ketone, ethyl acetate and γ-butyrolactone.

Examples of the mixed solvent include ethers, ethers and ketones, ethers and esters, and lactones.

Preferred mixed solvent systems are propylether and tetrahydrofuran, propylether and 1,4-dioxane, propylether and 1,3-dioxolane, isopropylether and tetrahydrofuran, isopropylether and 1,4-di Oxane, isopropyl ether and 1,3-dioxolane, propyl ether and methyl ether ketone, propyl ether and methyl isopropyl ketone, isopropyl ether and methyl ether ketone, isopropyl ether and methyl isopropyl ketone, and tetrahydrofuran Methyl ethyl ketone, tetrahydrofuran and methyl isopropyl ketone, 1,3-dioxolane and methyl ethyl ketone, 1,3-dioxolane and methyl isopropyl ketone, propyl ether and ethyl acetate, propyl ether and γ-buty Lolactone, isopropyl ether and ethyl acetate, isopropyl ether and γ-butyrolactone, tetrahydrofuran and ethyl acetate, tetrahydrofuran and γ-butyrolactone, 1,3-dioxolane and ethyl acetate, 1, 3-D Oxolane and γ-butyrolactone, methyl ethyl ketone and ethyl acetate, methyl ethyl ketone and γ-butyrolactone, methyl isopropyl ketone and ethyl acetate, methyl isopropyl ketone and γ-butyrolactone.

The amount of the reaction solvent varies depending on the target molecular weight, the monomer used, and the type of initiator used, but considering the solution of the monomer and the solvent, the monomer concentration is 20% by weight or more, preferably 30% by weight or more, and more preferably. A polymerization solvent is used so that it may be 40 weight% or more.

In addition, in this invention, what is shown below is a radical initiator which can be used for a polymerization reaction.

As a radical initiator, what is generally used, such as a peroxide and an azo initiator, can be used. Preferred are azo initiators.

Examples of azo initiators include 2,2-azobis (4-methoxy-2,4-dimethylbareronitrile), 2,2'-azobis (2-cyclopropylpropionitrile), and 2,2'-azo Bis (2,4-dimethylbareronitrile), 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'- Azobis (2-methyl-N-phenylpropionamidine) dihydrochloride, 2,2'-azobis (2-methyl-N-2-propenylpropionamidine) dihydrochloride, 2,2'-azo Bis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis {2-methyl-N- [1-1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, dimethyl2,2'-azobis (2-hydroxyethyl] propionamide}, dimethyl2,2'-azobis (2-methylpropionate), 4,4 '-Azobis (4-cyanovaleric acid) and 2,2'-azobis (2-hydroxymethyl) propionitrile).

Preferred is 2,2'-azobis (2,4-dimethylbareronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1 , 1'-azobis9cyclohexane-1-carbonitrile), dimethyl2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanobareric acid), 2 , 2'-azobis (2- (hydroxymethyl) propionitrile).

In the present invention, the polymer (resin) obtained after the polymerization reaction as described above can be recovered by the reprecipitation method. That is, after completion | finish of superposition | polymerization, a polymerization reaction liquid is thrown into a reprecipitating liquid and the target resin is collect | recovered in powder.

Examples of the reprecipitation liquid include alcohols, ethers, ketones, amides, esters and lactones, nitriles, hydrocarbons, and mixtures thereof.

Alcohols include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and 1-methoxy-2-propanol.

Examples of the ethers include propyl ether, isopropyl ether, butyl methyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane and 1,3-dioxane.

Acetone, methyl ethyl ketone, diethyl ketone, methyl isopropyl ketone, and methyl isobutyl ketone are mentioned as ketones.

Examples of the amides include N, N-dimethylformamide and N, N-dimethylacetamide.

Ester and lactones include ethyl acetate, methyl acetate, isobutyl acetate and γ-butyrolactone.

Examples of nitriles include acetonitrile, propionitrile and butyronitrile.

Examples of the hydrocarbons include straight chain such as pentane, hexane, heptane and octane, or branched hydrocarbons, cyclic hydrocarbons such as cyclopentane and cyclohexane, and aromatic hydrocarbons such as ketone and xylene.

Examples of the mixed liquid system include mixed liquid systems between alcohols, mixed liquid systems between hydrocarbons, hydrocarbons / alcohols, hydrocarbons / ethers, hydrocarbons / ketones, hydrocarbons / esters, and lactones.

Examples of mixed liquid systems between alcohols include methanol and ethanol, methanol and propanol, methanol and isopropanol, methanol and butanol, ethylene glycol and methanol, ethylene glycol and propanol, ethylene glycol and isopropanol, ethylene glycol and butanol, and 1-methoxy-2-. As a mixed liquid system between propanol and ethanol, 1-methoxy-2-propanol and propanol, 1-methoxy-2-propanol and isopropanol, 1-methoxy-2-propanol and butanol, and hydrocarbons, specifically, iso- Commercially available mixed solvents such as G, hexane and heptane, hexane and octane, hexane and cyclohexane, hexane and toluene, hexane and xylene, cyclohexane and toluene.

Other types of mixed solvents include hexane and propanol, hexane and isopropanol, hexane and butanol, hexane and tetrahydrofuran, hexane and acetone, hexane and methyl ethyl ketone, hexane and γ-butyrolactone. The mixing ratio of the mixed liquid system is 20/1 to 1/120.

Preferred reprecipitation solutions are commercially available mixed solvents such as hexane and isof-G, hexane and heptane, hexane and octane, hexane and cyclohexane, hexane and toluene, cyclohexane and toluene, hexane and propanol, hexane and isopropanol, hexane and butanol And hexane and tetrahydrofuran, hexane and acetone, hexane and methyl ethyl ketone, hexane and γ-butyrolactone.

Reprecipitation with a hydrocarbon solvent represented by reprecipitating hexane or butane described in Japanese Patent Application Laid-Open Nos. 9-73173, 10-207069, and 10-274852 is very dangerous, such as generating a constant voltage charging of the positive electrode, It is not good because of difficulty of workability.

Furthermore, the repetition of the reprecipitation as described in, for example, Japanese Patent Laid-Open No. 10-301285 unnecessarily increases the waste liquid, does not improve the working efficiency, and also worsens the edge roughness. In the present invention, the number of reprecipitations is preferably one to three times, and preferably one time.

The amount of the reprecipitation liquid is selected and set depending on the amount of solvent used in the polymerization, the kind and the type of the reprecipitation liquid, but it is 3 to 100 times the polymerization solution. Preferably it is 4 times-50 times, More preferably, it is 5 times-30 times. When this amount is small, it becomes difficult to separate from the powder to collect | recover, and work efficiency will worsen. In many cases, it is undesirable in terms of cost, such as an increase in waste liquid.

As described above, the molecular weight of the acid-decomposable resin is a weight average (Mw: polystyrene equivalent value by the GPC method), preferably 3,000 to 100,000, more preferably 4,000 to 70,000, and most preferably in the range of 5,000 to 50,000. . When molecular weight increases, heat resistance etc. improve, but since developability etc. fall, these balances are adjusted in an appropriate range.

In the positive resist composition of the present invention, the blending amount of the acid-decomposable resin in the entire resist composition is preferably 40 to 99.99% by weight in total solids, more preferably 50 to 99.97% by weight.

Below, the preferable specific example which combined the repeating structural unit of acid-decomposable resin which is (B) component is shown.

[3] (C) Compounds that generate acids by irradiation with actinic light or radiation (photoacid generators)

The photoacid generator used in the present invention is a compound that generates an acid by irradiation with actinic light or radiation.

Photoacid generators used in the present invention include photoinitiators of photocationic polymerization, photoinitiators of photo-radical polymerization, photochromic agents of pigments, photochromic agents, micro resists and the like. Particularly preferred are those compounds which generate an acid by g-ray, h-ray, i-ray, KrF excimer laser light), ArF excimer laser light, electron beam, X-ray, molecular beam or ion beam, and mixtures thereof. .

In addition, other photoacid generators used in the present invention include, for example, diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenium salts, arzonium salts, organic halogen compounds, and organic metal / organic halogens. The compound which produces | generates sulfonic acid by photolysis represented by a cargo, the photo-generation agent which has o-nitrobenzyl protecting group, an imino sulfonate, etc., a disulfone compound, a diazo keto sulfone, a diazo disulfone compound, etc. are mentioned.

And the compound which introduce | transduced the group or compound which generate | occur | produces an acid by these lights in the main chain or side chain of a polymer can be used.

See also V. N. R. Pillai, Synthesis, (1), 1 (1980), A. Abad et al, Tetra hedron Lett., (47), 4555 (1971), D. H. R. Barton et al, J. Chem. Soc., (C), 329 (1970), U.S. Patent No. 3,779,778, European Patent No. 126,712 and the like, can also be used a compound that generates an acid by light.

Among the compounds which decompose by irradiation of the electron beam and generate an acid, those used particularly effectively will be described below.

(1) An oxazole derivative represented by the following general formula (PAG1) substituted with a trihalomethyl group or an S-triazine derivative represented by the general formula (PAG2).

In the formula, R ²⁰¹ represents a substituted or unsubstituted aryl group, alkenyl group, and R ²⁰² represents a substituted or unsubstituted aryl group, alkenyl group, alkyl group, or -C (Y) ₃ . Y represents a chlorine atom or a fluorine atom.

Although the following compounds are mentioned in detail, it is not limited to these.

(2) Iodonium salt represented by the following general formula (PAG3), or sulfonium salt represented by general formula (PAG4).

Here, formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ , and R ²⁰⁵ each independently represent a substituted or unsubstituted alkyl group and an aryl group.

Z ^- is shown to mate the anion, for example BF ₄ ^-, AsF ₆ ^{-. _{PF 6 -, SbF 6 -,}} SiF 6 2-, ClO 4 -, CF 3 SO 3 - , such as perfluoro alkane sulfonic acid anion, a pentafluoro-benzenesulfonic acid anion, condensed naphthalene-1-sulfonic acid anion, such as Although polynuclear aromatic sulfonic acid anion, anthraquinone sulfonic acid anion, sulfonic acid group containing dye, etc. are mentioned, It is not limited to this.

In addition, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ , and Ar ¹ and Ar ² may be bonded to each other via a single bond or a substituent.

Although the compound shown below as a detailed example is not limited to this.

The onium salts represented by the formulas (PAG3) and (PAG4) are known and may be synthesized, for example, by the methods described in US Pat. Nos. 2,807,648 and 4,247,473, Japanese Patent Laid-Open No. 53-101,331.

(3) The disulfone derivative represented by the following general formula (PAG5) or the iminosulfonate derivative represented by the general formula (PAG6).

In the formulas, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group, an aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, arylene group.

Although the compound shown below is a detailed example, it is not limited to this.

(4) Diazodisulfone derivative represented by the following general formula (PAG7).

Here, R represents a straight chain, branched or cyclic alkyl group or an aryl group which may be substituted.

Although the compound shown below is mentioned as a detailed example, it is not limited to this.

The amount of such photoacid generator is generally used in the range of 0.001 to 40% by weight based on the solid content in the composition, but is preferably in the range of 0.01 to 20% by weight, more preferably 0.1 to 5% by weight. Used. If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity is lowered. If the amount of the photoacid generator is more than 40% by weight, the light absorption of the resist is excessively high, the profile is deteriorated or the process (especially the baking process) margin is narrowed. Not preferred.

[4] other ingredients

The positive resist composition of the present invention may contain other acid-decomposable dissolution inhibiting compounds, dyes, plasticizers, surfactants, photosensitizers, organic base compounds, and compounds that promote solubility in a developing solution, if necessary.

The positive resist composition of the present invention preferably contains a fluorine-based and / or silicon-based surfactant.

The positive resist composition of the present invention may contain any one or two or more of a fluorine-based surfactant, a silicone-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom.

By containing the acid-decomposable resin and the surfactant in the positive resist composition of the present invention, the line width of the pattern becomes further finer, the development defect is further improved, and the developability of the contact hole becomes more excellent.

As these surfactant, For example, Unexamined-Japanese-Patent No. 62-36663, Unexamined-Japanese-Patent No. 61-226745, Unexamined-Japanese-Patent No. 62-170950, No. 63-34540, No. 7-230165, Although Unexamined-Japanese-Patent No. 8-62834 and surfactant of Unexamined-Japanese-Patent No. 9-54432 and 9-5988 are mentioned, The following commercially available surfactant can also be used as it is.

Commercially available surfactants that can be used include, for example, Eftop EF301 and EF303 (manufactured by Shin-Akita Kasei Co., Ltd.), Florad FC430 and 431 (manufactured by Sumimoto 3M Company), Megafac F171, F173, F176, F189, and R08 (Dainipone Ink) & Chemicals Co., Ltd.) and fluorine-based surfactants or silicone-based surfactants such as Surflon S-382, SC101, 102, 103, 104, 105 and 106 (Asahi Glass Co., Ltd.), Toroidol S-366 (Toroid Chemical Co., Ltd.) There is. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) may also be used as the silicone surfactant.

The compounding quantity of surfactant is generally 0.01 weight%-2 weight%, Preferably it is 0.01 weight%-1 weight% based on solid content in the composition of this invention. Such surfactant can be used individually by 1 type or in combination of 2 or more types.

As said other surfactant which can be used, polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, polyoxyethylene oleyl ether, and polyoxy are mentioned in detail. Polyoxyethylene alkylaryl ethers such as ethylene octyl phenol ether and polyoxyethylene nonyl phenol ether, polyoxyethylene polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostea Latex, polyoxyethylene sorbitan triole And nonionic surfactants such as polyoxyethylene sorbitan fatty acid esters such as ate and polyoxyethylene sorbitan tristearate.

The compounding quantity of these surfactant is 2 weight% or less normally with respect to 100 weight% of solid content in the composition of this invention, Preferably it is 1 weight% or less.

Preferred organic basic compounds which can be used in the present invention are compounds which are more basic than phenol. Among these, a nitrogen-containing basic compound is preferable.

Where R²⁵⁰, R²⁵¹And R²⁵²May be the same or different and is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R²⁵¹And R²⁵²May combine with each other to form a ring.

(Wherein, R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶ may be the same or different and represent an alkyl group having 1 to 6 carbon atoms.)

Preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule, particularly preferred are those compounds containing both substituted and unsubstituted amino and nitrogen-containing atoms, or alkyls A compound having an amino group. Preferred detailed examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted imidazole, substituted or substituted Unsubstituted pyrazole, substituted or unsubstituted pyrazine, substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted pipepe Razin, substituted or unsubstituted aminomorpholine, substituted or unsubstituted aminoalkylmorpholine, and the like. Preferable substituents are amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group, cyano group.

Preferred examples of the nitrogen-containing basic compound include, specifically, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethyl Aminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine , 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl Piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- (2-aminoethyl) -pyrroli Dean, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2, 4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4. 0] Undeca-7-ene, 1,4-diazabicyclo [2.2.2] octane, 2,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydride Tertiary morpholine derivatives such as oxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU), and the inhibited amines described in Japanese Patent Application Laid-Open No. 1-52575 (for example, the above publications) Etc.), but are not limited to these.

Particularly preferred among the above examples are 1,5-diazabicyclo [4.3.0] nona-5-ene, 1,8-diazabicyclo [5.4.0] undeca-7-ene, 1,4-diazabi Agents such as cyclo [2.2.2] octane, 4-dimethylaminopyridine, hexanemethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines and CHMETU Suppressed amines, such as tertiary morpholines and bis (1,2,2,6,6-pentamethyl-4- piperidyl) sebacate, etc. are mentioned.

Among these, 1, 5- diazabicyclo [4.3.0] nona-5-ene and 1, 8- diazabicyclo [5. 4.0] underca-7-ene, 1,4-diazabicyclo [2.2.2] octane, 4-dimethylaminopyridine, hexamethylenetetramine, CHMETU, bis (1,2,2,6,6-pentamethyl 4-piperidyl) sebacate and the like are preferable.

These nitrogen-containing basic compounds may be used alone or in combination of two or more thereof. The usage-amount of a nitrogen-containing basic compound is generally 0.001-10 weight%, Preferably it is 0.01-5 weight% with respect to solid content of the whole composition of the photosensitive resin composition. If the amount of use is less than 0.001% by weight, the effect of adding the nitrogen-containing basic compound is not obtained. On the other hand, when the usage-amount exceeds 10 weight%, there exists a tendency for the fall of a sensitivity and the developability of a non-exposed part to deteriorate.

[5] manufacture and use of positive resist compositions

The positive resist composition of this invention is melt | dissolved in the solvent which melt | dissolves each said component, and apply | coats on a support body. As a solvent used here, ethylene dichloride, dichlorohexanone, dichloropentanone, 2-heptanone, (gamma) -butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-meth Oxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate Propyl pyruvate, N, N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable. These solvents can be used individually or in combination of 2 or more types.

Among the above, preferred solvents include 2-heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether And methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate, N-methylpyrrolidine, tetrahydrofuran and the like.

Such a positive resist composition of the present invention is applied onto a substrate to form a thin film. As for the film thickness of this thin film, 0.2-1.2 micrometers is preferable. In the present invention, a commercially available inorganic or organic antireflection film can be used if necessary.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, α-silicon, etc., and an organic film type made of a light absorber and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, a sputtering apparatus, etc. for film formation. As the organic antireflection film, for example, a condensation product of a diphenylamine derivative described in JP-A No. 7-69611 with a formaldehyde-modified melamine resin, an alkali-soluble resin, a light absorber, and a resin binder described in US Pat. No. 5294680; An acrylic resin antireflection film containing a methirolmelamine-based crosslinking agent, a carboxylic acid group described in Japanese Patent Application Laid-Open No. 6-118656, and simultaneously having an epoxy group and a light absorber in one molecule, and a metyrolmelamine group described in Japanese Patent Application Laid-Open No. 8-87115; The thing which consisted of a benzophenone type light absorber and the low molecular light absorber added to the polyvinyl alcohol resin of Unexamined-Japanese-Patent No. 8-179509 is mentioned.

In addition, as an organic antireflection film, DUV-30 series or DUV-40 series manufactured by Blue and Science, AC-2, AC-3 manufactured by Shippress, etc. may be used.

The resist liquid is applied to a substrate (e.g., silicon / silicon dioxide coating) used for the manufacture of a precision integrated circuit device (on a substrate coated with the antireflective film, if necessary), by a suitable coating method such as a spinner or a coater. After coating, a good resist pattern can be obtained by passing through a predetermined mask, exposing, baking and developing. Here, light of 150-250 nm wavelength is preferable as exposure light. Specifically, there are KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, electron beams, and the like.

As a developing solution, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, 1st amines, such as ethylamine and n-propylamine, diethylamine, di-n-butylamine, etc. Tertiary ammonium salts such as secondary amines, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide and tetraethylammonium hydroxide, Alkaline aqueous solutions, such as cyclic amines, such as a pyrrole and a piperidine, can be used.

Furthermore, alcohols and surfactants can be added to the alkaline aqueous solution in an appropriate amount.

Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to this Example.

(1) Synthesis of Resin (1) -1 (Dripping Method A)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 20%. 100 ml of a solution was prepared. To this solution was added 1 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) and 1 mol% of mercaptoethanol manufactured by Hwagwang Pure Chemical Co., Ltd. It was dripped at 10 ml of N, N- dimethylacetamide heated over 60 degreeC over. After dripping, the reaction liquid was heated and stirred for 3 hours. 1 mol% of V-65 was further added here, and the reaction liquid was heated and stirred for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder precipitated in 1.5 L of a mixed solvent of methanol / distilled water = 3/1 was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion measured by GPC (Shodex System-11) was 11900, and the area ratio of the monomer was 1.1%. In addition, the area ratio of the monomer used the RI detector (it is the same below).

(2) Synthesis of Resin (1) -2 (Dripping Method B)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 20%. 100 ml of a solution was prepared. To this solution was added 2 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) manufactured by Hwagwang Pure Chemical Co., Ltd., which was heated to 60 DEG C over 2 hours under a nitrogen atmosphere. It was dripped at 10 ml of N-dimethylacetamides. After completion of the dropwise addition, the reaction solution was heated and stirred for 3 hours. 1 mol% of V-65 was further added here, and the reaction liquid was heated and stirred for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the white powder precipitated in 1.5 L of a mixed solvent of methanol / distilled water = 3/1 was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 10200, and the area ratio of the monomer was 1.0%.

(3) Synthesis of Resin (1) -3 (Dripping Method C)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 20%. 100 ml of a solution was prepared. To this solution was added 1 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) and 1 mol% of mercaptoethanol manufactured by Hwagwang Pure Chemical Co., Ltd. It was dripped at 10 ml of N, N- dimethylacetamide heated over 60 degreeC over. After completion of the dropwise addition, the reaction solution was heated and stirred for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the white powder which was absent and precipitated in 1.5 L of a mixed solvent of methanol / distilled water = 3/1 was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion determined by GPC measurement was 12500, and the area ratio of the monomer was 2.4%.

(4) Synthesis of Resin (1) -4 (Dripping Method D)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 18%. 120 mL of a solution was prepared. 20% of this solution was taken and injected into the reaction vessel. Then, 2 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) manufactured by Hwagwang Pure Chemical Co., Ltd. was added to the remaining balance of 80%, and this was carried out over 2 hours under a nitrogen atmosphere. It dripped at the first solution ("20% solution") heated at 60 degreeC. After completion of the dropwise addition, the reaction solution was heated and stirred for 3 hours. 1 mol% of V-65 was further added here, and the reaction liquid was heated and stirred for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder precipitated in 1.5 L of isopropanol / distilled water = 3/1 mixed solvent was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion calculated by GPC measurement was 11100, and the area ratio of the monomer was 0.8%.

(5) Synthesis of Resin (1) -5 (Batch Method A)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 18%. 120 mL of a solution was prepared. The solution was heated and stirred at 60 ° C. under a nitrogen atmosphere to keep the temperature constant. Then, 2 moles of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) manufactured by Hwagwang Pure Chemical Co., Ltd. % Was added. After the addition, the reaction solution was heated and stirred for 3 hours. 1 mol% of V-65 was further added here, and the reaction liquid was heated and stirred for 3 hours. After the reaction was completed again, the reaction solution was cooled to room temperature, and the white powder which was absent and precipitated in 1.5 L of a mixed solvent of methanol / distilled water = 3/1 was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion calculated | required by GPC measurement was 12400, and the area ratio of the monomer was 4.5%.

(6) Synthesis of Resin (1) -R (Batch Method B): Comparative Example

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 18%. 120 mL of a solution was prepared. The solution was heated to 60 ° C. under a nitrogen atmosphere, stirred, and kept at a constant temperature. Then, 2 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) manufactured by Hwagwang Pure Chemical Co., Ltd. Was added. After the addition, the reaction solution was heated and stirred for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, and the white powder precipitated was recovered in 1.5 L of a mixed solvent of methanol / distilled water = 3/1.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion determined by GPC measurement was 13100, and the area ratio of the monomer was 5.8%.

(7) Synthesis of Resin (1) -6 (Division Addition Method A)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 18%. 120 mL of a solution was prepared. The solution was heated to 60 ° C. under a nitrogen atmosphere, and the temperature was kept constant. Then, 2 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) manufactured by Hwagwang Pure Chemical Co., Ltd. was 30 Add in 4 portions every minute. After the addition, the reaction solution was heated and stirred for 3 hours. 1 mol% of V-65 was further added here, and the reaction liquid was heated and stirred for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder precipitated in 1.5 L of methanol / distilled water = 3/1 mixed solvent was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion determined by GPC measurement was 12100, and the area ratio of the monomer was 3.1%.

(8) Synthesis of Resin (1) -7 (Partition-addition Method B)

2-ethyl-2-adamantyl methacrylate and butyrolactone methacrylate were added at a ratio of 40/60, dissolved in N, N-dimethylacetamide / tetrahydrofuran = 3/7, and the solid content concentration was 18%. 120 mL of a solution was prepared. The solution was heated to 60 ° C. under a nitrogen atmosphere, and the temperature was kept constant. Then, 2 mol% of V-65 (2,2'-azobis (2,4-dimethylbareronitrile)) manufactured by Hwagwang Pure Chemical Co., Ltd. was 30 Add in 4 portions every minute. After the addition, the reaction solution was heated and stirred for 4 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and white powder precipitated in 1.5 L of a mixed solvent of methanol / distilled water = 3/1 was recovered.

Polymer composition ratio determined from C ¹³ NMR was 44/56. In addition, the weight average molecular weight of the standard polystyrene conversion determined by GPC measurement was 12700, and the area ratio of the monomer was 4.3%.

The composition (2) -1 to (15) of the composition ratio, molecular weight, and residual monomer which were shown to the following Table 1 by operation similar to the said synthesis example were synthesize | combined. (The number of a repeating unit is The sequence number from the left side of the repeating unit 1,2 structure formula in the structure).

(9) Synthesis of Resin (16) -1 (Partition addition method, adding initiator)

A mixture of the following tetracyclododecene derivative (1-1) obtained by reaction of acrylic acid ester of 3-oxo-1,1-dimethylbutanol with cyclopentadiene and maleic anhydride in equimolar moles was injected into a separate flask, Heated at 80 ° C. under nitrogen atmosphere. After the reaction temperature was stabilized, 1 mol% of a radical initiator V-601 manufactured by Hwagwang Pure Chemical Co., Ltd. was added to initiate the reaction. After heating for 2 hours, a second mol of V-601 was added, followed by another 2 hours of heating, and another mol of V-601 was added for 12 hours. Then, 1 mole% of V-601 was added, heated for 3 hours, and then the reaction mixture was diluted twice with tetrahydrofuran, and then added to a mixed solution of hexane / isopropyl alcohol = 2/1 to give a white powder. Precipitated. The precipitated powder was collected by filtration and dried to obtain Resin (16) -1 as a target product.

When molecular weight was analyzed by GPC of obtained resin (16) -1, it was 9600 (weight average) in terms of polystyrene. In addition, the monomer area ratio remaining was 1.8%. In addition, the NMR spectrum confirmed that the ratio of the tetracyclododecene repeating unit of the resin (6) -1 to the maleic anhydride repeating unit was 1/1.

(10) Synthesis of Resin (16) -2 (Batch Addition, Initiator Added)

Into a separate flask was used a mixture of equimolar moles of the tetracyclododecene derivative (1-1) and maleic anhydride obtained by the reaction of acrylic acid ester of 3-oxo-1,1-dimethylbutanol and cyclopentadiene, Heated at 80 ° C. under a nitrogen atmosphere. After the reaction temperature was stabilized, 3 mol% of a radical initiator V-601 manufactured by Hwagwang Pure Chemical Co., Ltd. was added to initiate the reaction, and the reaction was heated for 12 hours. Then, 1 mole% of V-601 was added and heated for 3 hours, and then the reaction mixture was diluted twice with tetrahydrofuran, and then poured into a mixed solution of hexane / isopropyl alcohol = 2/1 to obtain white powder. Precipitated. The precipitated powder was collected by filtration and dried to obtain Resin (16) -2 as a target product.

The molecular weight was analyzed by GPC of the obtained resin (1-9), which was 9200 (weight average) in terms of polystyrene. In addition, the monomer area ratio remaining was 3.3%. In addition, the ratio of the tetracyclo dodecene repeating unit of the resin (16) -2 to the maleic anhydride repeating unit was 1/1 based on the NMR spectrum.

(11) Synthesis of Resin (16) -3 (load polymerization, initiator added)

Tetrahydrofuran / methylethyl was mixed in an equimolar mixture of the above-mentioned tetracyclododecene derivative (1-1) and maleic anhydride obtained by the reaction of acrylic acid ester of 3-oxo-1,1-dimethylbutanol and cyclopentadiene. It was dissolved in a mixed solvent of ketone = 1/1 to prepare a urine solution having a concentration of 60%. This 1/5 solution was injected into the detachable flask, and 1.5 mol% of radical initiators V-601 by Hwagwang Pure Chemical Co., Ltd. were added to the remaining solution. The reaction vessel was heated at 70 ° C. under a nitrogen stream, and after the reaction temperature was stabilized, 0.5 mol% of V-601 manufactured by Chemical Engineering Co., Ltd. was added to initiate the reaction. Then, the remaining monomer solution was added dropwise over 8 hours, and heated 4 hours after the end of the dropping. Subsequently, 1 mole% of V-601 was added and heated for 3 hours, and then the reaction mixture was added to a mixed solution of hexane / isopropyl alcohol = 5/1 to precipitate white powder. The precipitated powder was collected by filtration and dried to obtain Resin (16) -3 as a target product.

The molecular weight was analyzed by GPC of the obtained resin (16) -3, which was 7100 (weight average) in terms of polystyrene. In addition, the monomer area ratio remaining was 2.3%. In addition, the ratio of the tetracyclo dodecene repeating unit of the resin (16) -3 and the maleic anhydride repeating unit was 1/1 based on the NMR spectrum.

The resins ((17) -1 to (27) -2) shown in Table 2 were synthesized in the same manner as in the synthesis example (the number of repeating units is the repeating unit in the structure of the resins (17) to (27)). Display the sequence number from the left of.

In addition, the molar ratio, the weight average molecular weight, and the residual monomer amount of each repeating unit of the resins (17) -1 to (27) -2 are shown in Table 2.

Suzy Polymerization Polymerization solvent (weight ratio) Repeat unit (mol%) Molecular Weight (Mw) Remaining monomer (%) Re-immersion solution (weight ratio) One 2 3 (2) -1 Dropping method A e only 55 45 16300 0.8 b only (2) -2 Dropping method C e only 55 45 16900 1.9 b only (2) -3 Collective Law A e only 55 45 17400 4.0 b only (2) -4 Split Addition Method A d / e = 1/1 55 45 17100 3.2 a / c = 1/2 (3) -1 Dropping method B e / f = 2/1 53 47 12300 0.8 a / c = 1/3 (3) -2 Collective Law A f / h = 5/1 53 47 13300 4.2 a / i = 1/1 4 Dropping method A f / g = 6/4 47 53 13400 0.5 a / d = 1/3 (5) -1 Dropping method A d / f = 1/1 48 47 5 10300 0.6 b only (5) -2 Dropping method C d / f = 1/1 48 47 5 11100 2.3 b only (5) -3 Collective Law A d / f = 2/1 48 47 5 11900 3.9 b only (5) -4 Division Method B d / f = 1/1 48 47 5 11800 4.2 b only 6 Dropping method B e / g = 7/3 47 43 10 17300 0.8 a / b = 1/4 7 Dropping method A d / e = 4/6 57 41 2 16400 0.6 a / c = 1/3 8 Dropping method B e / f = 2/1 55 43 2 13300 0.4 a / d = 1/3 (9) -1 Dropping method A e / h = 5/2 46 54 12600 0.6 a / b = 1/3 (9) -2 Split Addition Method A e / h = 5/2 46 54 12900 3.1 a / b = 1/3 (10) -1 Dropping method A e / g = 2/1 47 49 4 11900 0.7 b only (10) -2 Collective Law A e / g = 2/1 47 49 4 12700 4.2 b only (10) -3 Split Addition Method A e / g = 2/1 47 49 4 12300 3.0 b only 11 Dropping method A d / e = 3/7 51 49 3 13100 0.9 a / c = 1/3 12 Dropping method d / e = 4/6 51 49 12400 1.2 a / c = 2/5 13 Dropping method B e only 54 46 12800 0.9 b only 14 Split Addition Method B e / f = 1/1 55 43 2 15700 1.0 b only 15 Split Addition Method A d / e = 5/3 54 42 4 13500 1.1 a / c = 1/3

Solvent a; Distilled water

Solvent b; Methanol

Solvent c; Isopropyl Alcohol

Solvent d; 1-methoxy-2-propanol

Solvent e; Tetrahydrofuran

Solvent f; Methyl ethyl ketone

Solvent g; N, N-dimethylacetamide

Solvent h; γ-butyrolactone

Solvent i; Acetonitrile

In addition, the initiators used are as follows.

2,2'-azobisisobutyronitrile; Resin 2, 6, 7

Dimethyl2,2'-azobis (2-methylpropionate); Resin 4, 14

Otherwise, 2,2'-azobis (2,4-dimethylbareronitrile)

Suzy Polymerization method * 1 Polymerization Solvent Alicyclic olefin Maleic Anhydride Maleic Acid Ester Mw Residual Monomer (%) Re-solvent solvent One 2 One 2 (17) -1 Batch none 50 50 9,300 4.6 c / h = 1/10 (17) -2 Split B none 50 50 8,500 3.9 c / h = 1/10 (18) -1 Dropping A c / f = 1/2 37 13 50 6,800 2.4 b / h = 1/6 (18) -2 Bulk A c / f = 1/2 37 13 50 7,300 2.9 b / h = 1/6 (19) -1 Division A b / e = 1/3 34 16 50 6,900 1.9 a / i = 1/7 (19) -2 Bulk A b / e = 1/3 34 16 50 7,200 2.6 a / i = 1/7 (20) -1 Division A none 50 28 22 8,700 1.9 a / h = 1/3 (20) -2 Split B none 50 28 22 8,900 4.4 a / h = 1/3 (21) -1 Division A b / f = 1/2 43 7 50 6,500 2.1 h / j = 3/1 (21) -2 Split B b / f = 1/2 43 7 50 6,900 4.7 h / j = 3/1 (22) -1 Bulk A none 44 6 50 7,900 2.6 c / h = 1/12 (22) -2 Batch none 44 6 50 8,100 4.9 c / h = 1/12 (23) -1 Dropping A c / d = 1/1 45 5 50 5,700 2.2 i only (23) -2 Dropping B c / d = 1/1 45 5 50 5,600 4.6 i only (24) -1 Division A none 38 3 9 50 9,700 2.1 f / h = 1/7 (24) -2 Batch e only 38 3 9 50 7,400 4.8 f / h = 1/7 (25) -1 Division A none 31 5 14 50 8,800 1.7 g / h = 1/15 (25) -2 Bulk A e / f = 1/1 31 5 14 50 6,600 2.9 g / h = 1/15 (26) -1 Bulk A none 33 7 10 50 8,200 2.7 h only (26) -2 Dropping A c / f = 2/1 33 7 10 50 6,400 2.2 h only (27) -1 Division A b / c = 1/1 30 6 14 50 5,500 1.8 e / h = 1/9 (27) -2 Bulk A none 30 6 14 50 8,600 2.5 e / h = 1/9

*One; Initiator batch addition, initiator addition == batch A

Initiator batch addition, no initiator addition = batch B

Initiator split add, initiator added = split A

Initiator split addition, no initiator addition

Add drop polymerization, add initiator = drop A

Drop polymerization, no addition of initiator

Solvent a; Isopropyl Alcohol

Solvent b; Isopropyl ether

Solvent c; Tetrahydrofuran

Solvent d; Acetone

Solvent e; Methyl ethyl ketone

Solvent f; Ethyl acetate

Solvent g; γ-butyrolactone

Solvent h; Hexane

Solvent i; Isof-g

Solvent j; toluene

In addition, the used initiator is radical initiator V-601 which is a product made from Chemical Engineering Pure Co., Ltd. mentioned above.

Examples 1 to 31 and Comparative Example 1

Preparation and Evaluation of Positive Resist Composition

1.4 g each of the resins shown in Table 3 synthesized in Synthesis Example,

0.2 g of photoacid generator shown in Table 3,

10 mg of organic basic compound (amine),

Surfactant (0.15g) was mix | blended as needed, each melt | dissolved in the propylene glycol monoethyl ether acetate in the ratio of 14 weight% of solid content, and it filtered with a 0.1 micrometer microfilter, and the positive resist of Examples 1-31 and a comparative example The composition was prepared.

Example No. Suzy Photoacid generator Amine Surfactants Sensitivity Edge roughness (nm) profile One (1) -1 One One W1 1.0 12 ○ 2 (1) -2 2 2 W2 1.0 12 ○ 3 (1) -3 2 One W3 1.0 13 ○ 4 (1) -4 One 2 W1 1.0 12 ○ 5 (1) -5 2 One W3 1.2 18 △ 6 (1) -6 One One W1 1.1 15 ○ 7 (1) -7 2 One W4 1.3 18 △ 8 (2) -1 One One W2 0.7 7 ○ 9 (2) -2 One One W4 0.9 7 ○ 10 (2) -3 2 One W1 1.0 16 △ 11 (2) -4 One 2 W2 0.9 13 ○ 12 (3) -1 2 One W1 1.0 12 ○ 13 (3) -2 One 2 W2 1.3 18 △ 14 4 2 One W3 0.9 10 ○ 15 (5) -1 2 2 W1 1.2 10 ○ 16 (5) -2 2 One W2 1.3 11 ○ 17 (5) -3 2 One W4 1.5 13 △ 18 (5) -4 One One W3 4.5 18 △ 19 6 2 One W1 0.6 6 ○ 20 7 2 One W1 0.8 9 ○ 21 8 2 One W2 0.7 7 ○ 22 (9) -1 One 2 W2 0.8 6 ○ 23 (9) -2 2 One W3 0.9 10 ○ 24 (10) -1 2 One W3 0.7 7 ○ 25 (10) -2 2 2 W1 1.0 16 △ 26 (10) -3 One One W2 0.9 12 ○ 27 11 2 2 W3 0.8 7 ○ 28 12 2 2 W1 0.9 7 ○ 29 13 2 One W2 0.8 7 ○ 30 14 2 One W3 0.8 6 ○ 31 15 One One W1 0.6 6 ○

Evaluation test

The obtained positive resist liquid was applied onto a silicon wafer using a spin coater, dried at 135 ° C. for 90 seconds to prepare a positive resist film of about 0.4 μm, and an ArF excimer laser (wavelength 193 nm, manufactured by ISI of NA = 0.6) was used. Exposure with an ArF stepper). Heat treatment after exposure was performed at 120 degreeC for 90 second, it developed in 2.38% aqueous tetramethylammonium hydroxide aqueous solution, wash | cleaned with distilled water, and the resist pattern profile was obtained.

About this, the sensitivity, the profile, and the edge roughness were evaluated as follows. The evaluation results are shown in Table 3.

[Sensitivity]: When the exposure amount of Example 1 was set to 1, the exposure amount which reproduces the line width of 0.18 micrometer was defined as the relative exposure amount.

[Profile]: The line profile of the 1/1 line & space type of 0.18 占 퐉 is observed with a scanning electron microscope, and the rectangular profile is O, and the tapered or small hem profile is Δ, and the complete tapered shape and hem The profile of the shape was evaluated by x.

Edge roughness: The edge roughness was measured using a side scanning scanning electron microscope (SEM) to perform edge roughness of the isolated pattern. The line pattern edge is detected at a plurality of positions in the measurement monitor, and the dispersion degree 3σ of the detected position is used as an index of the edge roughness. The smaller the value, the more preferable.

Examples 32-56 and Comparative Examples 2-3

Preparation and Evaluation of Positive Resist Composition

1.4 g each of the resins shown in Table 4 synthesized in Synthesis Example,

0.2 g of photoacid generator shown in Table 4,

10 mg of organic basic compound (amine),

If necessary, a surfactant (0.15 g) was added, and each was dissolved in propylene glycol monomethyl ether acetate at a ratio of 14% by weight of solids, and then filtered through a 0.1 μm microfilm to obtain Examples 32 to 56 and Comparative Examples 2-3. Positive resist composition was prepared. Table 4 shows specific details regarding the composition of the positive resist composition thus prepared. As the resin for the comparative example, the resin described in WO97 / 33198 was used as the resin R1 (the remaining monomer area ratio was 5.4%), and the resin of Synthesis Example 7 described in Japanese Patent Application Laid-Open No. 10-111569 was used as the resin R2 (the remaining monomer). Area ratio is 6.3%).

In addition, the positive resist composition prepared by the method described below was evaluated and the results are shown in Table 4.

In Table 4 below:

Photoacid generators are indicated by the numbers of the above examples.

As an amine, 1 represents 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), and 2 represents bis (1,2,2,6,6-pentamethyl-4-piperidyl Display the sebacate.

As a surfactant,

W1: Megafac F176 (product of Dainippon Ink Corporation) (fluorine system)

W2: Megafac R08 (manufactured by Dainippon Ink, Inc.) (fluorine-based and silicon-based)

W3: Polysiloxane Polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)

W4: polyoxyethylene nonyl phenyl ether

W5: Troisol S-366 (product of Troy Chemical Co., Ltd.)

Evaluation test

The obtained positive resist liquid was applied onto a silicon wafer using a spin coater, dried at 150 ° C. for 90 seconds to produce a positive resist film of about 0.4 μm, and an ArF excimer laser (wavelength of 193 nm, manufactured by ISI of NA = 0.6) was used. Exposure with an ArF stepper). The post-exposure heat treatment was performed at 150 ° C. for 90 seconds, developed in a 2.38% aqueous tetramethylammonium hydroxide solution and washed with distilled water to obtain a resist pattern profile.

About this, the sensitivity, the profile, and the edge roughness were evaluated as follows. The evaluation results are shown in Table 4.

[Sensitivity] When the exposure amount of Example 32 was set to 1, the exposure amount which reproduced the line width of 0.15 mu m was defined as the relative exposure amount.

[Profile]: A line profile of 1/1 line & space type of 0.15 占 퐉 is observed with a scanning electron microscope, and the rectangular profile is O, and the taper shape and small hem profile are Δ, and the complete taper shape and hemming The bottom shape profile was evaluated by x.

Edge roughness: The edge roughness was measured by using a scanning electron microscope (SEM) to perform edge roughness of an isolated pattern (0.15 µm). The line pattern edge is detected at a plurality of positions in the measurement monitor, and the dispersion degree 3σ of the detected position is used as an index of the edge roughness. The smaller the value, the more preferable.

Suzy Photoacid generator Amine Surfactants Sensitivity Edge roughness (nm) profile Example 32 (16) -1 PAG4-5 One W1 1.0 8 O 33 (16) -2 PAG4-8 2 W2 1.1 10 O 34 (16) -3 PAG4-33 One W3 1.0 8 O 35 (17) -1 PAG4-36 One W4 1.4 13 △ 36 (17) -2 PAG4-37 One W5 1.3 12 O 37 (18) -1 PAG4-36 One W5 0.9 10 O 38 (18) -2 PAG4-36 One W3 1.0 11 O 39 (19) -1 PAG4-36 One W1 0.8 9 O 40 (19) -2 PAG4-36 2 W2 0.9 11 O 41 (20) -1 PAG4-36 2 W5 1.0 10 O 42 (20) -2 PAG4-36 2 W4 1.1 13 △ 43 (21) -1 PAG4-36 2 W3 0.8 10 O 44 (21) -2 PAG4-36 2 W4 0.9 13 △ 45 (22) -1 PAG4-36 2 W5 0.8 11 O 46 (22) -2 PAG4-36 2 W4 0.9 14 △ 47 (23) -1 PAG4-36 2 W2 0.8 10 O 48 (23) -2 PAG4-5 One W1 0.9 13 △ 49 (24) -1 PAG4-6 One W2 0.8 10 O 50 (24) -2 PAG4-36 One W4 0.9 14 △ 51 (25) -1 PAG4-36 One W3 0.8 9 O 52 (25) -2 PAG4-36 One W5 0.8 12 O 53 (26) -1 PAG4-36 One W5 0.8 11 O 54 (26) -2 PAG4-36 2 W5 0.8 10 O 55 (27) -1 PAG4-36 2 W3 0.8 9 O 56 (27) -2 PAG4-36 2 W1 0.8 11 O Comparative Example 1 (1) -R One W1 2.0 28 × 2 R1 PAG4-5 none none 2.3 21 × 3 R2 PAG4-5 One none 2.4 19 ×

As is clear from the results shown in Tables 3 and 4, the positive resist composition of the present invention has sufficient sensitivity and improved profile, and also has excellent edge roughness.

The positive resist composition of the present invention is particularly suitable for far-ultraviolet light, in particular, ArF excimer laser light having a wavelength of 193 nm, high sensitivity, and excellent edge roughness. In addition, the resist pattern profile is excellent. Therefore, it is preferably used for lithography using far ultraviolet rays, including ArF excimer laser exposure.

Claims (10)

(A) contains an alkali-soluble group protected by one or more of the substructures containing alicyclic hydrocarbon groups represented by the following general formulas (pI) to (pVI), and the monomer component content is gel permeation chromatography (GPC). A resin which increases the dissolution rate in an alkaline developer by the action of an acid, which is 5% or less of the total pattern area of Wherein R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming an alicyclic hydrocarbon group together with carbon atoms. Display. If at least one of R ₁₂ to R ₁₄ or any one of R ₁₅ and R ₁₆ represents an alicyclic hydrocarbon, R ₁₂ to R ₁₆ are each independently a linear or branched alkyl or alicyclic hydrocarbon having 1 to 4 carbon atoms. Display the flag. If at least one of R ₁₇ to R ₂₁ represents an alicyclic hydrocarbon group, and any of R ₁₉ and R ₂₁ represents a straight or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 1 to 4 carbon atoms, ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or an alicyclic hydrocarbon group. If at least one of R ₂₂ to R ₂₅ represents an alicyclic hydrocarbon group, R ₂₂ to R ₂₅ each independently represent a linear or branched alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 1 to 4 carbon atoms.) (C) A positive resist composition comprising a compound that generates an acid upon irradiation with actinic light or radiation. The positive resist composition according to claim 1, wherein the resin (A) is a resin obtained by dropping a reaction solution containing a monomer and a radical initiator into a reaction solvent or a reaction solution containing a monomer and polymerizing the reaction. The positive resist composition according to claim 1, wherein the resin (A) is a resin obtained by subjecting a reaction solution containing monomers to a polymerization reaction by dividing a radical initiator over 30 minutes to 8 hours. The resin (A) according to any one of claims 1 to 3, wherein the resin (A) is polymerized by heating a reaction solution containing a monomer and a radical initiator, followed by re-adding the radical initiator and heating the polymerized reaction. It is obtained resin, The positive resist composition characterized by the above-mentioned. The resin of any one of claims 1 to 4, wherein the resin (A) is one or more of water and alcohols, water / alcohols, water / ethers, water / ketones and water after completion of the polymerization reaction. A positive resist composition, characterized in that it is a resin collected by pulverizing into at least one liquid selected from the group consisting of amides, water / esters or lactones, and water / nitriles. (B) (i) having at least one repeating structural unit selected from the repeating structural units represented by the following general formulas (Ia) and (Ib) and the repeating structural unit represented by the following general formula (II), (ii) a group which decomposes under the action of acid, and (iii) the content of monomer corresponding to the repeating structural unit constituting the resin is 5% or less of the total pattern area of gel permeation chromatography, and the action of acid causes an alkaline developer. A positive photoresist composition comprising a resin having an increased dissolution rate for the compound and (C) an acid which is generated by irradiation with actinic light and radiation. In formula (Ia): R ₁ and R ₂ are each independently a hydrogen atom, a cyano group, a hydroxyl group, -COOH, -COOR ₅ , -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ , an optionally substituted alkyl group or an alkoxy group Or a cyclic hydrocarbon group or the following -Y group. X represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-. Here, R <_5> represents the alkyl group which may have a substituent, a cyclic hydrocarbon group, or the following -Y group. R ₆ represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. A represents a single bond or a divalent linking group. -Y group; (In the -Y group, R ₂₁ to R ₃₀ each independently represent a hydrogen atom or an alkyl group which may have a substituent. A and b represent 1 or 2.) In formula (Ib): Z ₂ represents -O- or -N (R ₃ )-, wherein R ₃ represents a hydrogen atom, a hydroxyl group or -OSO ₂ -R ₄ . R ₄ represents an alkyl group, haloalkyl group, cycloalkyl group or camphor residue. In formula (II): R ₁₁ and R ₁₂ each independently represent a hydrogen atom, a cyano group, a halogen atom or an alkyl group which may have a substituent. Z includes two bonded carbon atoms (C-C) and represents an atomic group for forming an alicyclic structure which may have a substituent. A compound according to claim 6, wherein in the general formula (II), Z represents an atomic group for forming a piercing alicyclic structure which may include two carbon atoms (CC) bonded thereto and may have a substituent. Positive photoresist composition. The positive photoresist composition according to claim 6, wherein the general formula (II) is the following general formula (II-A) or general formula (II-B). In formulas (II-A) and (II-B): R ₁₃ to R ₁₆ are each independently a hydrogen atom, a halogen atom, a cyano group, -COOH, -COOR ₅ (R ₅ has the same meaning as described above), a group decomposed by the action of an acid, -C (= O ) -XAR ₁₇ or an alkyl or cyclic hydrocarbon group which may have a substituent. In addition, two or more of R ₁₃ to R ₁₆ may be bonded to each other to form a ring. n represents 0 or 1. Here, X and A have the same meanings as above. R ₁₇ is -COOH, -COOR ₅ , -CN, a hydroxyl group, an alkoxy group which may have a substituent, -CO-NH-R ₆ , -CO-NH-SO ₂ -R ₆ (R ₅ , R ₆ are respectively The same meaning as described above) or the -Y group. The resin of claim 6, wherein the resin of (B) is subjected to a polymerization reaction by heating a solution containing a monomer and a radical initiator corresponding to the repeating structural unit constituting the resin, followed by further adding a radical initiator and heating to It is a polymer obtained by performing a polymerization reaction, The positive photoresist composition characterized by the above-mentioned. The resin of claim 6, wherein the resin of (B) is a mixture of water, alcohols, ethers, ketones, amides, esters, lactones, nitriles, hydrocarbons, and mixed solvents thereof. A positive photoresist composition, characterized in that it is a polymer which is added to at least one solvent selected from a solvent group consisting of precipitated polymer and then recovered in powder.